TW202104485A - Composite sheet for forming protective film and method for manufacturing semiconductor chip having protective film including an antifouling sheet and a film for forming a protective film formed on one side of the antifouling sheet - Google Patents

Abstract

A composite sheet for forming a protective film of the present embodiment includes an antifouling sheet and a film for forming a protective film formed on one side of the antifouling sheet, wherein the maximum value of the width of the composite sheet for forming a protective film is from 155mm to 194mm, from 205mm to 250mm, from 305mm to 350mm, or from 455mm to 500mm, and a test piece of the aforementioned antifouling sheet having a width of 15mm can be extended by 15% or more, and the tensile strength at 10% of elongation is 4.0N/15mm or more.

Description

Composite sheet for forming protective film, and manufacturing method of semiconductor wafer with protective film

The present invention relates to a composite sheet for forming a protective film and a method for manufacturing a semiconductor wafer with a protective film. This application claims priority based on Japanese Patent Application No. 2019-115790 filed in Japan on June 21, 2019, and the content of the application is cited herein.

In the manufacturing process of a semiconductor device, a protective film is sometimes used to protect a workpiece that needs to be processed in order to obtain a target. For example, when a semiconductor device is manufactured using a packaging method called a face down method, a semiconductor wafer having electrodes such as bumps on the circuit formation surface is used as a workpiece, in order to suppress the semiconductor wafer or as a semiconductor wafer. The semiconductor wafer of the divided circle has cracks, and a protective film is sometimes used to protect the semiconductor wafer or the inner surface of the semiconductor wafer on the opposite side to the circuit formation surface. In addition, in the manufacturing process of the semiconductor device, the semiconductor device panel is used as a workpiece, and in order to prevent the panel from warping or cracking, a protective film is sometimes used to protect any part of the panel. Here, the "semiconductor device panel" refers to a panel that is operated during the manufacturing process of the semiconductor device. As a specific example of the panel, a semiconductor device in a state where one or more electronic components are sealed by a sealing resin can be cited. The device is such that a plurality of these semiconductor devices are arranged in a circular, rectangular, or other shape in a planar shape, and are electrically connected to each other to form a panel.

In order to form such a protective film, for example, a composite sheet for protective film formation is used which includes a support sheet and further includes a protective film formation film for forming a protective film on one side of the support sheet. The film for forming a protective film may function as a protective film by curing, or may function as a protective film in an uncured state. In addition, the support sheet can be used to fix a workpiece provided with a protective film forming film or a protective film. For example, when a semiconductor wafer is used as a workpiece, the support sheet can be used as a dicing sheet required for dividing the semiconductor wafer into semiconductor wafers. As the support sheet, for example, a support sheet provided with a base material and an adhesive layer provided on one surface of the aforementioned base material; a support sheet composed of only the base material, and the like. When the support sheet is provided with an adhesive layer, the adhesive layer is arranged between the base material and the protective film formation film in the composite sheet for protective film formation.

In the case of using the above-mentioned composite sheet for forming a protective film, first, the film for forming a protective film in the composite sheet for forming a protective film is attached to the target portion of the work. Then, the workpiece in the state provided with such a composite sheet for forming a protective film is processed to obtain a workpiece processed product. For example, when the work is a semiconductor wafer, the protective film formation film in the protective film formation composite sheet is attached to the aforementioned inner surface of the semiconductor wafer. Then, for example, the semiconductor wafer is divided into semiconductor wafers, the protective film formation film or protective film is cut, and the semiconductor wafer provided with the cut protective film formation film or protective film on the inner surface is separated from the support sheet and picked up. The order of dividing the semiconductor wafer into semiconductor wafers and cutting the protective film forming film or the protective film may be performed first according to the purpose, or may be performed at the same time. When the protective film formation film is curable, the curing of the protective film formation film (that is, the formation of the protective film) may be performed at any timing. Through the above steps, a semiconductor wafer with a protective film formed by providing a protective film on the inner surface of the semiconductor wafer is obtained as a workpiece to be processed.

As such a composite sheet for forming a protective film, for example, a film for a semiconductor device is disclosed that includes a substrate, an adhesive layer, and a film for the inner surface of a flip chip semiconductor (corresponding to the aforementioned film for forming a protective film), and can suppress Winding traces (also referred to as "rolling traces") are generated when being wound into a roll (refer to Patent Document 1).

In the foregoing, the case of using the protective film forming composite sheet provided with the support sheet and the protective film forming film has been described, but the protective film forming film that does not constitute the protective film forming composite sheet may also be used. In this case, for example, when the work is a semiconductor wafer, it is only necessary to harden the protective film formation film if necessary by attaching a protective film forming film that is not integrated with the support sheet due to the inner surface of the semiconductor wafer. It is sufficient to form a protective film. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2016-213236.

[The problem to be solved by the invention]

When dividing a semiconductor wafer, it is necessary to fix the semiconductor wafer in a state with a composite sheet for forming a protective film in a dividing device. For example, when a dicing blade is used to divide (cut) a semiconductor wafer, the semiconductor wafer and the protective film forming composite sheet are fixed by a jig such as a ring frame in the dicing device.

On the other hand, printing is sometimes performed by irradiating a film for forming a protective film attached to the inner surface of a semiconductor wafer with laser light (in this specification, sometimes referred to as "laser printing"). In this case, before dividing the semiconductor wafer, a semiconductor wafer with a composite sheet for forming a protective film or a film for forming a protective film that is not integrated with the support sheet must be placed on the semiconductor wafer for laser printing. The device (in this manual, sometimes referred to as "laser printing device").

However, a semiconductor wafer provided with a general composite sheet for forming a protective film on the inner surface cannot be installed in a general laser printing device because the composite sheet for forming a protective film, particularly the support sheet in the composite sheet, is too large. In addition, when handling a semiconductor wafer with a protective film forming film that is not integrated with the support sheet on the inner surface, if the protective film forming film is on the opposite side to the semiconductor wafer side If it is exposed, unexpected foreign matter will adhere to the exposed surface and cause problems. The reason is that the film for forming a protective film is relatively soft and has moderate adhesiveness.

This section describes the laser printing of the protective film forming film on the semiconductor wafer with the protective film forming film on the inner surface. However, the procedure for handling the semiconductor wafer with the protective film forming film is not Limited to the steps of laser printing. As such a step, for example, there are other steps such as the step of transporting the semiconductor wafer provided with the protective film forming film to the target location, and the same problem as the case of the laser printing step is performed.

Moreover, the film for a semiconductor device (corresponding to the film for forming a protective film described above) disclosed in Patent Document 1 cannot solve these problems.

The object of the present invention is to provide a composite sheet for forming a protective film, including a protective film forming film for forming a protective film on the inner surface of a semiconductor wafer, and forming a protective film on the inner surface before dividing the semiconductor wafer When handling with a filmed semiconductor wafer, it is possible to prevent unintended foreign matter from adhering to the protective film forming film, and has characteristics suitable for this purpose. [Means to solve the problem]

The present invention provides a composite sheet for forming a protective film, which is used to be attached to the inner surface of a semiconductor wafer to form a protective film on the inner surface; the composite sheet for forming a protective film includes an anti-fouling sheet and formed on the anti-fouling A film for forming a protective film on one side of a sheet; the film for forming the protective film can form the protective film; the composite sheet for forming a protective film relative to the attachment of the semiconductor wafer to the composite sheet for forming a protective film The maximum width in the direction parallel to the surface is 155mm to 194mm, 205mm to 250mm, 305mm to 350mm, or 455mm to 500mm; the test piece of the aforementioned antifouling sheet with a width of 15mm is made, and the following tensile test is performed. That is, under the temperature condition of 18°C to 28°C, the initial chuck spacing is set to 100mm, and the test piece is stretched at a speed of 200mm/min in a direction parallel to the surface of the test piece. The test piece can be extended by 15% or more, and the tensile strength of the aforementioned test piece when it is extended by 10% is 4.0N/15mm or more. In the composite sheet for forming a protective film of the present invention, the antifouling sheet may be the aforementioned protection for preventing unexpected foreign matter from adhering to the inner surface of the semiconductor wafer when the composite sheet for forming a protective film is used. Film sheet for film formation. In the composite sheet for forming a protective film of the present invention, the antifouling sheet may have a transparency of 100 or more.

In addition, the present invention provides a method for manufacturing a semiconductor chip with a protective film, which is to manufacture a semiconductor chip with a protective film and a protective film provided on the inner surface of the semiconductor chip; the protective film is made of the protective film The protective film formation film in the formation composite sheet is formed; when the protective film formation film is curable, the cured product of the protective film formation film is a protective film, and the protective film formation film is not In the case of curability, the film for forming the protective film after being attached to the inner surface of the semiconductor wafer before being divided into the semiconductor wafer is a protective film; the manufacturing method of the semiconductor chip with the protective film includes: first attaching The step is to stretch the composite sheet for forming a protective film in a direction parallel to the attaching surface to the semiconductor wafer in the composite sheet for forming a protective film while stretching the composite sheet for forming a protective film The protective film forming film in is attached to the entire inner surface of the semiconductor wafer that is smaller in size than the protective film forming film, thereby fabricating a composite sheet provided with the protective film forming composite sheet on the inner surface of the semiconductor wafer The first layered body; the first cutting step is to cut the composite sheet for forming the protective film in the first layered body along the outer periphery of the semiconductor wafer, thereby manufacturing it on the inner surface of the semiconductor wafer There is the second laminated body of the composite sheet for forming the protective film after cutting; the operation step is to operate the second laminated body; the second attaching step is after the operation step and the second layer after the operation The adhesive sheet is attached to the side of the antifouling sheet in the laminate on the side opposite to the side of the protective film forming film or the protective film; the dividing step is after the second attaching step, dividing the semiconductor wafer, Thus, a semiconductor wafer is produced; the second cutting step is to cut the protective film forming film or protective film after the second attaching step; and the pickup step is to provide the cut protective film forming film Or the semiconductor chip of the protective film is pulled away from the laminated sheet including the antifouling sheet and the adhesive sheet and picked up; in the first attaching step, the composite sheet for forming the protective film is formed relative to the protective film The maximum width of the composite sheet in the direction parallel to the attachment surface of the semiconductor wafer is relative to the semiconductor wafer relative to the attachment of the composite sheet for forming the protective film in the semiconductor wafer The maximum width of the attached surface in the parallel direction becomes 101.1% to 129.3%; when the film for forming a protective film is curable, there is a curing step, which is followed by the above-mentioned operation step to form the protective film The film is hardened, thereby forming a protective film. In the method for manufacturing a semiconductor wafer with a protective film of the present invention, the operation step may be a printing step of printing by irradiating the film for forming a protective film in the second layered body with laser light. [Efficacy of invention]

According to the present invention, there is provided a composite sheet for forming a protective film, which is provided with a protective film forming film for forming a protective film on the inner surface of a semiconductor wafer, and before dividing the semiconductor wafer, the inner surface is formed with a protective film When handling with a filmed semiconductor wafer, it is possible to prevent unintended foreign matter from adhering to the protective film forming film, and has characteristics suitable for this purpose.

◇Composite sheet for forming protective film The composite sheet for forming a protective film according to an embodiment of the present invention is used for attaching to the inner surface of a semiconductor wafer to form a protective film on the inner surface; the composite sheet for forming a protective film includes an antifouling sheet and is formed on the inner surface of the semiconductor wafer. The film for forming a protective film on one side of the antifouling sheet; the film for forming the protective film can form the protective film; the composite sheet for forming the protective film is relative to the semiconductor wafer in the composite sheet for forming the protective film The maximum width of the attachment surface in the parallel direction is 155mm to 194mm, 205mm to 250mm, 305mm to 350mm, or 455mm to 500mm; a test piece of the aforementioned antifouling sheet with a width of 15mm is made, and the following tensile test is performed , That is, under the temperature condition of 18°C to 28°C, the initial chuck spacing is set to 100mm, and the test piece is stretched at a speed of 200mm/min in a direction parallel to the surface of the test piece , The aforementioned test piece can be extended by 15% or more (in this specification, this characteristic is sometimes referred to as "15% extensibility"), and the tensile strength when the aforementioned test piece is extended by 10% (in this specification, sometimes referred to as "Tensile strength at 10% elongation") 4.0N/15mm or more.

The protective film formation film in the composite sheet for protective film formation of the present embodiment is not cured or hardened into a cured product, whereby a protective film for protecting the inner surface of the semiconductor wafer can be formed. In addition, the antifouling sheet is used at the time of handling (at the time of use) of the composite sheet for forming a protective film, and prevents unexpected foreign matter from adhering to the film for forming a protective film.

The composite sheet for forming a protective film of the present embodiment has the maximum width in a direction parallel to the attaching surface to the semiconductor wafer in the composite sheet for forming a protective film within a specific range as described above, and It is suitable for handling a semiconductor wafer with a protective film forming film on the inner surface before the semiconductor wafer is divided. For example, when a semiconductor wafer equipped with a protective film forming film is handled in an arbitrary device (if one example is given, the protective film forming film is laser-printed in a laser printing device described later), even if the device When it does not correspond to the use of a jig such as a ring frame for fixing a semiconductor wafer, the composite sheet for forming a protective film of the present embodiment can also be handled without any problem in such an apparatus. In addition, in this specification, unless otherwise specified, the "width of the protective film forming composite sheet" means the aforementioned "protective film forming composite sheet relative to the semiconductor wafer in the protective film forming composite sheet" The attachment surface has a width in a parallel direction".

The aforementioned antifouling sheet in the composite sheet for forming a protective film of the present embodiment has good cutting suitability. The reason is that the aforementioned test piece of the antifouling sheet has the aforementioned tensile strength at 10% elongation when subjected to the aforementioned tensile test. In addition, as described later, the composite sheet for forming a protective film is stretched in a direction parallel to the attaching surface to the semiconductor wafer in the composite sheet for forming a protective film while the composite sheet for forming a protective film is stretched. When the protective film forming film in the sheet is attached to the entire inner surface of the semiconductor wafer, the antifouling sheet will not be cut or wrinkles will be generated, and it will have good attachment adaptability. The reason is that the aforementioned test piece of the antifouling sheet has the above-mentioned 15% elongation when subjected to the aforementioned tensile test. Therefore, the cutting suitability and adhesion suitability of the protective film forming composite sheet are also good, and the protective film forming can be adjusted well by cutting according to the size of the semiconductor wafer to be attached to the protective film forming composite sheet. The size of the composite sheet. That is, the composite sheet for forming a protective film of this embodiment has characteristics suitable for the antifouling purpose of the film for forming a protective film.

[Maximum width of composite sheet for protective film formation] The shape of the composite sheet for forming a protective film, that is, the planar shape of the composite sheet for forming a protective film, when viewed from the side of the attaching surface to the semiconductor wafer in the foregoing composite sheet for forming a protective film, is not particularly The limitation can be appropriately adjusted according to the planar shape of the attachment surface of the composite sheet for forming the protective film in the semiconductor wafer. For example, for a semiconductor wafer having a circular planar shape, a composite sheet for forming a protective film having a circular planar shape can be used. In this case, the maximum value of the width of the above-mentioned composite sheet for forming a protective film becomes the diameter of the circle as the above-mentioned planar shape.

The maximum value of the width of the composite sheet for protective film formation is 155 mm to 194 mm, 205 mm to 250 mm, 305 mm to 350 mm, or 455 mm to 500 mm. These four numerical ranges correspond to semiconductor wafers. The maximum value of the width of the semiconductor wafer in a direction parallel to the attachment surface of the protective film forming composite sheet is 150 mm, 200 mm, 300 mm, or 450 mm. The size of such a composite sheet for forming a protective film can be referred to as a wafer size. Among the aforementioned maximum widths of these semiconductor wafers, values other than "450mm" are based on the "Standard specification for dimensional properties of silicon wafers with specular surfaces); Author: Silicon Technology Committee (Silicon Technologies Committee), Management Committee on Information Technology Standardization (Managing Committee on Information Technology Standardization); Issued by: Japan Electronic and Information Technology Industries Association" so-called "JEITA EM-3602" (2002 (Issued in July 2007) the "diameter" of the "silicon mirror wafer" specified in 150mm, 200mm and 300mm. For example, in this field, diameters of 150mm, 200mm, 300mm, or 450mm are customarily referred to as 6 inches, 8 inches, 12 inches, or 18 inches. In addition, in this specification, unless otherwise specified, the "width of the semiconductor wafer" means the aforementioned "semiconductor wafer with respect to the surface of the semiconductor wafer that is attached to the protective film forming composite sheet. The width in the parallel direction". For example, in the case of a semiconductor wafer whose planar shape is a circular shape, the maximum width of the aforementioned semiconductor wafer becomes the diameter of the circle of the aforementioned planar shape.

The maximum width of the composite sheet for forming a protective film of 155 mm to 194 mm is 103.3% to 129.3% relative to the maximum width of the semiconductor wafer of 150 mm. The maximum width of the composite sheet for forming a protective film of 205 mm to 250 mm is 102.5% to 125% relative to the maximum width of the 200 mm semiconductor wafer. The maximum width of the composite sheet for forming a protective film of 305mm to 350mm is 101.7% to 116.7% relative to the maximum of the width of the semiconductor wafer of 300mm. The maximum width of the composite sheet for forming a protective film of 455 mm to 500 mm is 101.1% to 111.1% relative to the maximum width of the semiconductor wafer of 450 mm. Based on these relationships, for example, regardless of whether the maximum width of the semiconductor wafer is 150 mm, 200 mm, 300 mm, or 450 mm, the maximum width of the composite sheet for forming a protective film relative to the maximum width of the semiconductor wafer may be 101.1% to 129.3%.

When the maximum width of the composite sheet for forming a protective film is 155mm to 194mm, the maximum width of the semiconductor wafer (150mm) may be, for example, 103.3% to 125.3% (155mm to 188mm), and 103.3 Any one of% to 115.3% (155mm to 173mm). When the maximum width of the composite sheet for forming a protective film is 205mm to 250mm, the maximum width (200mm) of the semiconductor wafer may be, for example, 102.5% to 120% (205mm to 240mm), and 102.5 % To 115% (205mm to 230mm). When the maximum width of the composite sheet for forming a protective film is 305mm to 350mm, the maximum value (300mm) of the width of the semiconductor wafer may be, for example, 101.7% to 114% (305mm to 342mm), and 101.7 Any one of% to 111% (305mm to 333mm). When the maximum width of the protective film forming composite sheet is 455 mm to 500 mm, the maximum width of the semiconductor wafer (450 mm) may be, for example, 101.1% to 110.4% (455 mm to 497 mm), and 101.1 Any one of% to 110% (455mm to 495mm). And, for example, regardless of the maximum width of the semiconductor wafer being 150 mm, 200 mm, 300 mm, and 450 mm, the maximum width of the composite sheet for forming a protective film can be 101.1% relative to the maximum width of the semiconductor wafer. To 125.3%, 101.1% to 120%, and 101.1% to 114%.

[15% extensibility of antifouling sheet (test piece)] The 15% extensibility of the aforementioned test piece can be confirmed in accordance with JIS K 7127:1999 (ISO527-3:1995) and JIS K 7161:1994 (ISO5271:1993). More specifically, it is as follows. First, make a test piece of the anti-fouling sheet with a width of 15mm. The length of the test piece is not particularly limited as long as the tensile test described later can be performed, and it may be 120 mm or more, for example. Then, the test piece is fixed to a stretching mechanism (such as a clamp) for stretching the test piece in the length direction. At this time, the initial chuck interval before the test piece is stretched (in other words, the distance between the fixed positions of the test piece before the test piece is stretched by the stretching mechanism) is set to 100 mm. In addition, perform the following tensile test: under the temperature condition of 18°C to 28°C, from this state, the test piece is moved in the length direction of the test piece by the stretching mechanism at a speed of 200mm/min (in this manual, Sometimes called "stretching speed") Stretching. At this time, as long as the test piece does not break and elongates by 15% or more in the tensile direction of the test piece, the test piece has 15% extensibility. On the other hand, if the test piece breaks before it stretches by 15% or more in the tensile direction of the test piece, the test piece does not have 15% elongation. Here, the so-called "test piece elongation of 15% or more" means that _{when the length of the test piece before the start of the tensile test is set to L 0} and the length of the test piece during the tensile test is set to L ₁ , the formula is satisfied: (L ₁ －L ₀ )/L ₀ ×100≧15. In this embodiment, the aforementioned test piece has 15% extensibility.

In this embodiment, the aforementioned antifouling sheet and the aforementioned test piece made of the aforementioned antifouling sheet are both resin layers (in other words, films or sheets) that use resin as a constituent material, and have an MD direction and an MD direction according to the method of manufacturing the resin layer. TD direction. The "MD direction" and "TD direction" in this case have the same meanings as usual in this field. That is, the so-called "MD direction" means the machine direction of the resin during the molding of the resin layer (Machine Direction), and the so-called "TD direction" means the direction of travel (MD direction) of the resin during the molding of the resin layer. Transverse Direction.

In this embodiment, when the above-mentioned tensile test is performed, regardless of the direction in which the test piece is stretched, the test piece has 15% elongation. Therefore, the test piece has, for example, 15% extensibility in both the MD direction and the TD direction of the test piece.

[Tensile strength of anti-fouling sheet (test piece) at 10% elongation] The tensile strength of the aforementioned test piece at 10% elongation is the tensile strength when the aforementioned test piece is not broken but is extended by 10% in the tensile direction of the aforementioned test piece. In this embodiment, the tensile strength of the aforementioned test piece at 10% elongation is 4.0N/15mm or more.

In this embodiment, when the above-mentioned tensile test is performed, regardless of the direction of the tensile direction, the tensile strength of the aforementioned test piece at 10% elongation is 4.0 N/15 mm or more. Therefore, for example, in both the MD direction and the TD direction of the test piece, the tensile strength of the test piece at 10% elongation is 4.0N/15mm or more.

In terms of the above-mentioned antifouling sheet having better cutting adaptability, the tensile strength at 10% elongation of the aforementioned test piece is preferably 4.5N/15mm or more, more preferably 5.0N/15mm or more, for example, Any of 10N/15mm or more, 15N/15mm or more, and 20N/15mm or more. In addition, in this embodiment, when the above-mentioned tensile test is performed in two directions of the MD direction and the TD direction of the test piece, it is preferable to perform the tensile test in either or both of these two directions so that 10 of the test pieces are The tensile strength at% elongation is more than the aforementioned lower limit, and more preferably in both directions, the tensile strength at 10% elongation of the test piece is greater than the aforementioned lower limit.

The upper limit of the tensile strength at 10% elongation of the aforementioned test piece is not particularly limited. For example, in terms of easier manufacture of the antifouling sheet, the aforementioned tensile strength may also be 470N/15mm or less. For example, when cutting the antifouling sheet or the composite sheet for forming a protective film, the abrasion of the cutting blade used in the cutting is suppressed, the tensile strength of the aforementioned test piece at 10% elongation It is preferably 360N/15mm or less, for example, it may be any of 250N/15mm or less, 200N/15mm or less, 150N/15mm or less, 100N/15mm or less, and 50N/15mm or less. In addition, in this embodiment, when the above-mentioned tensile test is performed in the MD direction and the TD direction of the test piece, the test piece can be elongated by 10% in either or both of these two directions. The tensile strength at this time is less than the aforementioned upper limit, and it may be in both directions so that the tensile strength at 10% elongation of the test piece is less than the aforementioned upper limit.

The tensile strength at 10% elongation of the aforementioned test piece can be suitably adjusted to be within the range set by any combination of any of the above-mentioned lower limit and any upper limit. For example, in one embodiment, the aforementioned tensile strength is preferably 4.0N/15mm to 470N/15mm, more preferably 4.5N/15mm to 470N/15mm, for example, 10N/15mm to 470N/15mm, 15N/15mm to Any one of 470N/15mm, and 20N/15mm to 470N/15mm. In addition, in one embodiment, the aforementioned tensile strength is preferably 4.0N/15mm to 360N/15mm, for example, 4.0N/15mm to 250N/15mm, 4.0N/15mm to 200N/15mm, 4.0N/15mm to 150N /15mm, 4.0N/15mm to 100N/15mm, and 4.0N/15mm to 50N/15mm. In addition, in one embodiment, the aforementioned tensile strength is preferably 4.5N/15mm to 360N/15mm, for example, 10N/15mm to 250N/15mm, 10N/15mm to 200N/15mm, 10N/15mm to 150N/15mm, Any one of 15N/15mm to 100N/15mm, and 20N/15mm to 50N/15mm. In addition, in this embodiment, when the above-mentioned tensile test is performed in two directions of the MD direction and the TD direction of the test piece, it is preferable to perform the tensile test in either or both of these two directions so that 10 of the test pieces are The tensile strength at% elongation is in the above numerical range, more preferably in both directions, so that the tensile strength at 10% elongation of the test piece is in the above numerical range.

The 15% elongation and the tensile strength at 10% elongation of the aforementioned test piece (anti-fouling sheet) can be adjusted, for example, by adjusting the constituent materials or thickness of each layer of the anti-fouling sheet, such as the substrate, adhesive layer, etc. described later, or The formation method of each layer can be adjusted.

The aforementioned test piece used to confirm the 15% elongation and the tensile strength at 10% elongation can be made from the antifouling sheet at the stage before the composite sheet for forming a protective film, or it can be used for forming a self-protective film. The composite sheet is taken out of the anti-fouling sheet and made from the anti-fouling sheet. No matter what kind of antifouling sheet is used, the 15% elongation and the tensile strength at 10% elongation are the same.

When the aforementioned test piece satisfies the aforementioned 15% elongation and 10% elongation tensile strength conditions, when the aforementioned antifouling sheet is cut, the generation of burrs in the cut surface is suppressed, showing excellent Cut off suitability. In addition, the composite sheet for forming a protective film provided with such an antifouling sheet also exhibits excellent cutting suitability. When the composite sheet for forming a protective film of the present embodiment is cut in a stage after being attached to a semiconductor wafer, the antifouling sheet and the composite sheet for forming a protective film are required to have the above-mentioned tensile properties. The reason is that the composite sheet for forming a protective film is attached to the semiconductor wafer in a state of being stretched in a direction parallel to the attaching surface to the semiconductor wafer in the composite sheet for forming a protective film to maintain It is cut off in this state. The composite sheet for forming a protective film of this embodiment has the above-mentioned stretching characteristics, and when it is cut in a stretched state in the stage after being attached to a semiconductor wafer, the composite sheet for forming a protective film Since the cutability of the sheet is good, the roughness of the cut surface of the composite sheet for forming a protective film is suppressed.

[Clearance of antifouling sheet] The transparency of the antifouling sheet is not particularly limited. For example, it can be 30 or more, preferably 100 or more, and can be any of 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, and 400 or more. The higher the transmission clarity, the more clear printing can be achieved when laser printing is performed by irradiating the protective film forming film with laser light through the antifouling sheet. In addition, the visibility of the laser printing formed on the protective film formation film or the protective film through the antifouling sheet (in this specification, it may be referred to as "laser printing visibility") becomes higher.

The upper limit of the transparency of the antifouling sheet is not particularly limited. For example, in terms of easier manufacture of the anti-fouling sheet, the aforementioned transmission clarity may be 500 or less.

The transparency of the aforementioned antifouling sheet can be suitably adjusted to be within a range set by any combination of the above-mentioned lower limit and upper limit. For example, in one embodiment, the aforementioned transmission clarity may be 30 to 500, preferably 100 to 500, and may be 150 to 500, 200 to 500, 250 to 500, 300 to 500, 350 to 500, and 400 to 500 Of any kind.

The transparency of the aforementioned antifouling sheet means that the width of the slit through which the irradiated light is transmitted is set to 0.125mm, 0.25mm, 0.5mm, 1mm, and 2mm in accordance with JIS K 7374:2007, as described in the following examples. Of the five types, in each case, the total value of the evaluation value when the evaluation value of the image clarity (image clarity) is obtained for the antifouling sheet.

Hereinafter, each layer constituting the aforementioned composite sheet for forming a protective film will be described in detail.

◎Anti-fouling film The aforementioned antifouling sheet may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the antifouling sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

In addition, in this specification, it is not limited to the case of the antifouling sheet. The so-called "multilayers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, and only a part of the layers may be the same." , The so-called "multi-layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other."

The antifouling sheet may be transparent or opaque, and may be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, the antifouling sheet preferably allows energy ray to pass through. For example, laser printing is performed on a protective film forming film or protective film attached to the inner surface of a semiconductor wafer, and in order to confirm the printing through the antifouling sheet, the antifouling sheet is preferably transparent. For example, in order to optically inspect the protective film forming film in the protective film forming composite sheet or the protective film forming film or the protective film attached to the inner surface of the semiconductor wafer through the antifouling sheet, the antifouling sheet is preferably Transparent.

In this specification, the so-called "energy line" refers to electromagnetic waves or charged particle beams with energy quantum. Examples of energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In addition, in this specification, the term "energy ray curability" means the property of curing by irradiation with energy rays, and the term "non-energy ray curability" means the property of not curing even if energy rays are irradiated.

As an antifouling sheet, for example, a sheet provided with a substrate and an adhesive layer formed on one surface of the substrate; a sheet composed of only the substrate, and the like. When using a composite sheet for forming a protective film with an adhesive layer, the antifouling sheet and the protective film can be easily adjusted by changing the characteristics of the adhesive layer, more specifically, whether the adhesive layer is hardened or not. Adhesion between the film or its cured product. When using a composite sheet for forming a protective film composed of only a base material, since such a composite sheet for forming a protective film is inexpensive, a semiconductor wafer with a protective film can be manufactured inexpensively.

Hereinafter, an example of the overall configuration of the composite sheet for forming a protective film will be described for each type of antifouling sheet while referring to the drawings. In addition, in the drawings used in the following description, in order to make it easier to understand the characteristics of the present invention and for convenience, the main parts may be enlarged and shown, and the dimensional ratios of the constituent elements are not limited to the actual ones.

Fig. 1 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 101 for forming a protective film shown here includes an antifouling sheet 10 and a film for forming a protective film formed on one side of the antifouling sheet 10 (in this specification, sometimes referred to as the "first side") 10a 13.

The antifouling sheet 10 includes a base material 11 and an adhesive layer 12 formed on one surface of the base material 11 (in this specification, it may be referred to as a "first surface") 11a. That is, the antifouling sheet 10 is formed by stacking the base material 11 and the adhesive layer 12 in the thickness direction of these layers.

That is, the composite sheet 101 for forming a protective film is composed of a base material 11, an adhesive layer 12, and a film 13 for forming a protective film in order in the thickness direction of these layers. In addition, the composite sheet 101 for forming a protective film is further provided with a release film on the surface 13a opposite to the adhesive layer 12 side of the film 13 for forming a protective film (in this specification, sometimes referred to as the "first surface") 13a 15.

One side or both sides of the base material before processing used in the antifouling sheet may become an uneven surface having an uneven shape. When the both sides of the substrate are smooth surfaces with low concavity and convexity, depending on the constituent material of the substrate, when the substrate is wound into a roll, the contact surfaces of the substrates may stick and stick. It becomes difficult to use. However, if at least one of the contact surfaces of the substrates is a concave-convex surface, the area of the contact surface becomes small, and therefore blocking is suppressed. Therefore, in the composite sheet 101 for forming a protective film, the first surface 11a of the substrate 11 and the surface of the substrate 11 opposite to the first surface 11a side (in this specification, sometimes referred to as "second surface ") Either or both sides of 11b can be concave and convex. In addition, when only one of the first surface 11a and the second surface 11b of the substrate 11 is a concave-convex surface, either surface can be selected as the concave-convex surface.

In the composite sheet 101 for forming a protective film, the first surface 10a of the antifouling sheet 10 and the surface of the adhesive layer 12 opposite to the substrate 11 side (in this specification, it may be referred to as the "first surface") The meaning of 12a is the same. In addition, the first surface 13a of the protective film forming film 13 has the same meaning as the attaching surface 101a to the semiconductor wafer in the protective film forming composite sheet 101.

The first surface 13a of the protective film formation film 13 is preferably capable of covering the entire area of the inner surface of the semiconductor wafer to be attached to the protective film formation composite sheet 101.

_{The maximum value of the width W 101} of the protective film forming composite sheet 101 is 155 mm to 194 mm, 205 mm to 250 mm, 305 mm to 350 mm, or 455 mm to 500 mm. To the substrate 11, adhesive layer 12 and the protective film is different from each other when there is a case where the maximum width of each of those film 13, wherein the maximum value to the maximum value of the width W _101. In the cross section shown in FIG. 1, the width of each of the base material 11, the adhesive layer 12, and the film 13 for protective film formation is the same. In addition, when the composite sheet for forming a protective film is provided with a release film like the composite sheet for forming a protective film 101, in this embodiment, the width of the composite sheet for forming a protective film (for example, W ₁₀₁ ) does not include the width of the release film. width.

In the composite sheet 101 for forming a protective film, the aforementioned test piece of the antifouling sheet 10 has 15% extensibility. Furthermore, the tensile strength of the aforementioned test piece of the antifouling sheet 10 at 10% elongation is 4.0 N/15 mm or more.

The overall shape of the protective film forming composite sheet 101 when looking down from above the protective film forming composite sheet 101 in a plan view, in other words, when looking down from the first surface 13a side of the protective film forming film 13 (That is, the overall planar shape of the composite sheet 101 for forming a protective film) is not particularly limited. When the composite sheet 101 for forming a protective film is viewed from above, the shape of each of the base material 11, the adhesive layer 12, and the film 13 for forming a protective film (that is, the planar shape of the first surface of each) may all be the same, or All may be different, and only a part may be the same, but it is preferable that all are the same. In addition, when the composite sheet 101 for forming a protective film is viewed from above, the size of each of the substrate 11, the adhesive layer 12, and the film 13 for forming a protective film (that is, the area of the first surface of each) may all be the same. All of them may be different, or only some of them may be the same. However, the mutual error of these sizes (error of area) is preferably within 90%, more preferably within 95%, and still more preferably within 98%.

For example, in terms of particularly high versatility of the composite sheet 101 for forming a protective film, the aforementioned planar shape of the entire composite sheet 101 for forming a protective film is preferably a rectangular shape or a band shape. The composite sheet 101 for forming a protective film whose planar shape is a belt shape is suitable for being wound in a roll shape along the longitudinal direction of the composite sheet 101 for forming a protective film, for storage.

FIG. 2 is a plan view schematically showing an example of a composite sheet 101 for forming a protective film whose overall planar shape is a rectangular shape or a strip shape. In addition, in the drawings following FIG. 2, the same components as those shown in the previously described diagrams are assigned the same reference numerals as in the previously described diagrams, and detailed descriptions of the components are omitted.

In the composite sheet 101 for forming a protective film shown in FIG. 2, for example, the entire area of the _{composite sheet 101 for forming a protective film (in a direction orthogonal to the direction of the width W 101 in FIG. 2) is} The width of each of the material 11, the adhesive layer 12, and the protective film forming film 13 may all be the same. That is, in the composite sheet 101 for forming a protective film, the adhesive layer 12 may be provided on the entire surface of the first surface 11a of the base material 11, and the protective film forming film may be provided on the entire surface of the first surface 12a of the adhesive layer 12 13.

In the composite sheet 101 for forming a protective film shown in FIG. 2, for example, in the longitudinal direction of the composite sheet 101 for forming a protective film, a plurality of composite sheets for forming a protective film for attaching to a semiconductor wafer can be cut out.

The aforementioned planar shape of the entire composite sheet 101 for forming a protective film may be another shape that does not correspond to any of a rectangular shape and a band shape.

The composite sheet 111 for forming a protective film shown in FIG. 3 is equivalent to the composite sheet 101 for forming a protective film shown in FIG. In the form of the laminate of the protective film formation film 13, punching is performed in the longitudinal direction of the protective film formation composite sheet 101, and the composite sheet obtained by removing the part that does not correspond to the aforementioned laminate.

The composite sheet 111 for forming a protective film shown in FIG. 3 is in the longitudinal direction of the release film 15 whose planar shape is rectangular or tape-like, and a plurality of substrates 11 and adhesives whose planar shapes are all round are arranged. The layer 12 and the layered product 1111 of the film 13 for protective film formation are comprised. The laminate 1111 itself can be said to be equivalent to a composite sheet for forming a protective film, and it can be said that it is a composite sheet for forming a protective film of another shape whose planar shape does not correspond to either a rectangular shape or a band shape.

In addition, FIG. 3 shows that the width of the aforementioned laminate 1111 (in other words, the width W _{111 of the} protective film forming composite sheet 111) is slightly narrower than the width of the release film 15, but the width of the aforementioned laminate 111 (protective film _{The width W 111} ) of the forming composite sheet 111 may be the same as the width of the release film 15.

The composite sheet 101 for forming a protective film shown in FIG. 2 is superior to the composite sheet 111 for forming a protective film shown in FIG. 3 in terms of storage properties and usability. More specifically, the composite sheet 101 for forming a protective film can make all the layers (the base material 11, the adhesive layer 12, the film 13 for forming a protective film, and the release film 15) constituting the composite sheet 101 for forming the protective film viewed in a plan view. Different from the composite sheet for protective film formation 101 and the composite sheet for protective film formation 111, when the composite sheet 101 for forming a protective film and the composite sheet 111 for forming a protective film are wound into a roll shape and stored, the generation of curl marks can be suppressed and the storage performance is excellent. In addition, when attaching the protective film forming composite sheet 111 to the semiconductor wafer, the aforementioned laminate 1111 must be aligned with the semiconductor wafer, but when attaching the protective film forming composite sheet 101 to the semiconductor wafer There is no need for such alignment, and the composite sheet 101 for forming a protective film is excellent in usability.

The protective film forming composite sheet 101 is a state in which the release film 15 is removed, and the first surface 13a of the protective film forming film 13 in the protective film forming composite sheet 101 is attached to a semiconductor wafer (illustration omitted) Shown) inside.

4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention.

The composite sheet 102 for forming a protective film shown here is similar to the composite sheet 101 for forming a protective film shown in FIG. 1 except that it does not have the adhesive layer 12 (that is, the antifouling sheet is composed of only a base material). the same. In other words, the composite sheet 102 for forming a protective film is the same as the composite sheet 101 for forming a protective film except that it has the antifouling sheet 20 without the adhesive layer 12 instead of the antifouling sheet 10.

In the protective film forming composite sheet 102, the first surface 11a of the base material 11 and the surface of the antifouling sheet 20 on the side of the protective film forming film 13 (in this specification, sometimes referred to as the "first surface") 20a means the same. In addition, the first surface 13a of the protective film forming film 13 has the same meaning as the attaching surface 102a to the semiconductor wafer in the protective film forming composite sheet 102.

_{The maximum value of the width W 102} of the composite sheet 102 for forming a protective film is 155 mm to 194 mm, 205 mm to 250 mm, 305 mm to 350 mm, or 455 mm to 500 mm. In the composite sheet 102 for forming a protective film, the aforementioned test piece of the antifouling sheet 20 has 15% extensibility. Furthermore, the tensile strength of the aforementioned test piece of the antifouling sheet 20 at 10% elongation is 4.0 N/15 mm or more.

The protective film forming composite sheet 102 is a state in which the release film 15 is removed, and the first surface 13a of the protective film forming film 13 in the protective film forming composite sheet 102 is attached to a semiconductor wafer (illustration omitted) Shown) inside.

The composite sheet for forming a protective film of this embodiment is not limited to the composite sheet for forming a protective film shown in FIGS. 1 to 4. For example, in the composite sheet for forming a protective film of this embodiment, part of the composite sheet for forming a protective film shown in FIGS. 1 to 4 may be changed or deleted within the range that does not impair the effects of the present invention, or it may be modified from FIG. 1 To the composite sheet for forming a protective film shown in FIG. 4, other structures are further added.

For example, the composite sheet for forming a protective film of this embodiment may include other layers that are not equivalent to any of the base material, the adhesive layer, the film for forming a protective film, and the release film. The type of the aforementioned other layer and the arrangement position of the aforementioned other layer are not particularly limited, and can be arbitrarily selected according to the purpose.

The composite sheet for forming a protective film provided with the aforementioned other layers also preferably satisfies the conditions of the shape and size described above. That is, the overall shape (planar shape of the entire composite sheet for forming a protective film) when the composite sheet for forming a protective film is provided with the other layer as viewed from above is not particularly limited. In addition, when the composite sheet for forming a protective film is viewed from above, the shapes of the base material, the adhesive layer, the film for forming the protective film, and the aforementioned other layers may all be the same, or all of them may be different, or only a part may be the same, but Preferably they are all the same. In addition, when the composite sheet for forming a protective film is viewed from above, the size of each of the base material, the adhesive layer, the film for forming the protective film, and the other layers described above may all be the same, or all may be different, or only a part of the same may be the same. However, the mutual error of these sizes (error of area) is preferably within 90%, more preferably within 95%, and still more preferably within 98%.

Next, each layer constituting the antifouling sheet will be described in more detail.

○Substrate The substrate is in a sheet shape or a film shape, and as a constituent material of the substrate, various resins can be cited, for example. Examples of the aforementioned resin include polyethylenes such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- (Meth) acrylate copolymers, ethylene-norbornene copolymers and other vinyl copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine Resin obtained from ethylene as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate Diesters, poly(ethylene-2,6-naphthalate), wholly aromatic polyesters with aromatic cyclic groups in all constituent units; copolymers of two or more of the aforementioned polyesters; poly(methyl) ) Acrylate; Polyurethane; Polyacrylic urethane; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene ether; Polyphenylene sulfide; Poly turquoise; polyether ketone and so on. Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester. In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or more of the aforementioned resins as exemplified above; ionic polymerization using one or more of the aforementioned resins exemplified in the foregoing Modified resins such as materials.

The resin constituting the base material may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

The base material may be composed of one layer (single layer) or two or more layers. In the case of being composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the substrate is preferably 8 μm to 300 μm, more preferably 10 μm to 260 μm, for example, can be any of 10 μm to 200 μm, 10 μm to 160 μm, and 10 μm to 120 μm. When the thickness of the base material is in this range, the flexibility of the composite sheet for forming a protective film and the adhesion to the semiconductor wafer or the semiconductor wafer are further improved. Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of the substrate composed of multiple layers means the total thickness of all layers constituting the substrate.

As explained above, the antifouling sheet (the aforementioned test piece) has 15% extensibility, and the substrate has extensibility. The antifouling sheet provided with such a substrate is suitable for placing the antifouling sheet on a protective film or a film for forming a protective film relative to the antifouling sheet in the pickup step in the method of manufacturing a semiconductor wafer with a protective film described later When the side surface is expanded in a parallel direction, while picking up a semiconductor chip with a protective film. Examples of the constituent material of such a substrate having excellent extensibility include polyolefins such as polyethylene and polypropylene, and polyesters such as polyethylene terephthalate.

The base material may contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the aforementioned main constituent materials such as resins.

The substrate may be transparent or opaque, and may be colored according to the purpose, and other layers may be vapor-deposited. For example, when the film for forming a protective film has energy ray curability, it is preferable that the base material transmits energy ray. For example, in order to perform laser printing on a protective film forming film or protective film attached to the inner surface of a semiconductor wafer, in order to confirm the printing through an antifouling sheet, the base material is preferably transparent. For example, in order to optically inspect the protective film formation film in the protective film formation composite sheet or the protective film formation film or the protective film attached to the inner surface of the semiconductor wafer through the antifouling sheet, the base material is preferably transparent .

In order to improve the adhesion between the substrate and the layer provided on the substrate (for example, the adhesive layer, the film for forming a protective film, or the aforementioned other layers), the surface of the substrate may be subjected to sandblasting, solvent treatment, etc. Concave-convex treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; lipophilic treatment; hydrophilic treatment, etc. In addition, a primer treatment may be applied to the surface of the substrate.

The base material can be manufactured by a known method. For example, a resin-containing substrate can be manufactured by molding a resin composition containing the aforementioned resin.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or film and contains an adhesive. Examples of the aforementioned adhesives include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. It is preferably an acrylic resin.

In addition, in this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resins include not only resins with adhesive properties, but also resins that exhibit adhesiveness by being used in combination with other ingredients such as additives, and those that exhibit adhesiveness by the presence of heat or water as a trigger. Resin etc.

The adhesive layer may be composed of one layer (single layer) or two or more layers. In the case of being composed of multiple layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited.

The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer.

The adhesive layer may be transparent or opaque, and may be colored according to the purpose. For example, when the film for forming a protective film has energy ray curability, the adhesive layer preferably allows the energy ray to pass through. For example, in order to perform laser printing on a protective film forming film or protective film attached to the inner surface of a semiconductor wafer, in order to confirm the printing through the antifouling sheet, the adhesive layer is preferably transparent. For example, in order to optically inspect the protective film forming film in the protective film forming composite sheet or the protective film forming film or the protective film attached to the inner surface of the semiconductor wafer through the antifouling sheet, the adhesive layer is preferably Transparent.

The adhesive layer can be formed using an energy ray-curable adhesive or may be formed using a non-energy ray-curing adhesive. That is, the adhesive layer may be either energy ray curable or non-energy ray curable. The energy-ray curable adhesive layer can easily adjust the physical properties before and after curing.

[Adhesive composition] The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is coated on the surface to be formed of the adhesive layer, and dried as necessary, thereby forming the adhesive layer on the target site. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the aforementioned components in the adhesive layer. In this specification, the "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, and for example, a temperature of 15°C to 25°C, etc. can be mentioned. A more specific method of forming the adhesive layer will be described in detail later together with the method of forming other layers.

The adhesive composition can be applied by a known method. For example, methods using the following various coaters can be cited: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coater, etc.

When the adhesive layer is provided on the substrate, for example, the adhesive composition is coated on the substrate and dried if necessary, thereby laminating the adhesive layer on the substrate. In addition, when the adhesive layer is provided on the substrate, for example, the adhesive layer can also be laminated on the substrate by applying the adhesive composition on the release film, and drying it if necessary, thereby An adhesive layer is formed in advance on the release film, and the exposed surface of the adhesive layer is attached to a surface of the substrate. In this case, the release film may be removed at any timing during the manufacturing process or the use process of the composite sheet for forming a protective film.

The drying conditions of the adhesive composition are not particularly limited, and when the adhesive composition contains a solvent described later, it is preferable to heat and dry. In addition, the adhesive composition containing the solvent is preferably dried under the conditions of 70°C to 130°C and 10 seconds to 5 minutes, for example.

When the adhesive layer is energy ray curable, as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive composition, for example, the following adhesive compositions can be cited: The adhesive composition (I-1) contains a non-energy-ray curable adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive resin (I-1a)") and an energy-ray curable compound; The adhesive composition (I-2) is contained in the side chain of the non-energy-ray-curable adhesive resin (I-1a). The side chain of the unsaturated group is introduced into the energy-ray-curable adhesive resin (I-2a) (below , Sometimes simply referred to as "adhesive resin (I-2a)"); adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

[Adhesive composition (I-1)] The aforementioned adhesive composition (I-1) contains a non-energy-ray curable adhesive resin (I-1a) and an energy-ray curable compound as described above.

[Adhesive resin (I-1a)] The aforementioned adhesive resin (I-1a) is preferably an acrylic resin. As said acrylic resin, the acrylic polymer which has at least the structural unit derived from the alkyl (meth)acrylate is mentioned, for example. The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

Examples of the aforementioned alkyl (meth)acrylate include alkyl (meth)acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the aforementioned alkyl group is preferably linear or branched. shape. As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth) Nonadecyl acrylate, eicosyl (meth)acrylate, etc.

In terms of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from the alkyl (meth)acrylate alkyl ester having a carbon number of 4 or more. In addition, in terms of further improving the adhesive force of the adhesive layer, the carbon number of the aforementioned alkyl group is preferably 4-12, more preferably 4-8. In addition, the alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms is preferably an alkyl acrylate.

The aforementioned acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. As the aforementioned functional group-containing monomer, for example, the following monomers are exemplified: the aforementioned functional group reacts with the crosslinking agent described later to become the starting point of crosslinking, or the aforementioned functional group reacts with the following unsaturated group-containing monomer. The unsaturated group in the compound reacts, and the unsaturated group can be introduced into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. That is, as a monomer containing a functional group, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing an epoxy group, and the like can be cited.

Examples of the hydroxyl-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Allyl alcohol and other non-(meth)acrylic unsaturated alcohols (unsaturated alcohols without (meth)acrylic acid skeleton), etc.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); the anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (formula Group) carboxyalkyl acrylate and the like.

The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer relative to the total amount of the structural unit is preferably 1% to 35% by mass, more preferably 2% to 32% by mass, especially Preferably, it is 3% by mass to 30% by mass.

The aforementioned acrylic polymer may have structural units derived from other monomers in addition to structural units derived from alkyl (meth)acrylates and functional group-containing monomers. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylates and the like. Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

The aforementioned other monomers constituting the aforementioned acrylic polymer may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

The aforementioned acrylic polymer can be used as the aforementioned non-energy-ray-curable adhesive resin (I-1a). On the other hand, a resin obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group (energy-ray polymerizable group) can be used as the aforementioned energy-ray curable property The adhesive resin (I-2a).

The adhesive composition (I-1) contains only one type of adhesive resin (I-1a), or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected .

In the adhesive composition (I-1), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-1) is preferably 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass.

[Energy ray hardening compound] Examples of the aforementioned energy ray curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by energy ray irradiation. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (Meth)acrylate such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylic amine methyl Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above. In terms of relatively large molecular weight and difficult to reduce the storage elastic modulus of the adhesive layer, the energy ray curable compound is preferably (meth)acrylate urethane, (meth)acrylate urethane formic acid Ester oligomers.

The aforementioned energy ray curable compound contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned adhesive composition (I-1), the ratio of the content of the aforementioned energy ray curable compound to the total mass of the adhesive composition (I-1) is preferably 1% to 95% by mass, more preferably 5 mass% to 90 mass%, particularly preferably 10 mass% to 85% by mass.

[Crosslinking agent] When using the aforementioned acrylic polymer having a functional group-containing monomer-derived structural unit in addition to the structural unit derived from the alkyl (meth)acrylate as the adhesive resin (I-1a), adhesion The agent composition (I-1) preferably further contains a crosslinking agent.

The crosslinking agent reacts with the functional group, for example, to crosslink the adhesive resins (I-1a). Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents with glycidyl groups); aziridines such as hexa[1-(2-methyl)-aziridinyl] triphosphoryl triazine Crosslinking agent (crosslinking agent with aziridin group); metal chelate crosslinking agent such as aluminum chelate (crosslinking agent with metal chelate structure); isocyanurate crosslinking agent Agent (crosslinking agent with isocyanuric acid skeleton) and so on. The cross-linking agent is preferably an isocyanate-based cross-linking agent in terms of improving the cohesive force of the adhesive and improving the adhesive force of the adhesive layer, and ease of availability.

The crosslinking agent contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned adhesive composition (I-1), the content of the crosslinking agent relative to the content of the adhesive resin (I-1a) is 100 parts by mass, preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass It is 20 parts by mass, particularly preferably 0.3 parts by mass to 15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. Even if the adhesive composition (I-1) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the aforementioned photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds; benzyl Sulfide compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diacetone compounds such as diacetin; benzophenone; benzophenone; benzophenone; 2,4-diethylthioxanthone ; 1,2-Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and the like. In addition, as the aforementioned photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.03 to 20 parts by mass relative to the content of the aforementioned energy ray curable compound 100 parts by mass 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.

[Other additives] The adhesive composition (I-1) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention. Examples of the aforementioned other additives include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Known additives such as reaction delay agents, crosslinking accelerators (catalysts), and interlayer transfer inhibitors.

In addition, the so-called reaction delay agent means, for example, to prevent the effect of the catalyst mixed in the adhesive composition (I-1) from causing unexpected progress in the adhesive composition (I-1) during storage. The component of the cross-linking reaction. As the reaction delay agent, for example, a compound that forms a chelate complex by a chelate against a catalyst can be cited, and more specifically, a compound having two or more carbonyl groups (-C(= O)-) Compounds. In addition, as the interlayer transfer inhibitor, for example, a component for suppressing the transfer of a component contained in a layer adjacent to the adhesive layer, such as a film for forming a protective film, to the adhesive layer. As the interlayer transfer inhibitor, the same component as the target of the transfer inhibition can be cited. For example, when the target of the transfer inhibition is the epoxy resin in the film for forming a protective film, the same kind of epoxy resin can be used.

The other additives contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

The content of the other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected according to the type of the other additives.

[Solvent] The adhesive composition (I-1) may also contain a solvent. By containing a solvent, the adhesive composition (I-1) can improve the coating suitability to the surface to be coated.

The aforementioned solvent is preferably an organic solvent. Examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (I-1a) can be directly used in the adhesive composition (I-1) without removing the solvent used in the production of the adhesive resin (I-1a), or it can be used for adhesive During the manufacture of the agent composition (I-1), a solvent of the same or different type as the solvent used in the manufacture of the adhesive resin (I-1a) is separately added.

The solvent contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

The content of the solvent in the adhesive composition (I-1) is not particularly limited, and may be appropriately adjusted.

[Adhesive composition (I-2)] The aforementioned adhesive composition (I-2) is contained in the side chain of the non-energy-ray-curable adhesive resin (I-1a) as described above, and the unsaturated group is introduced into the energy-ray-curable adhesive resin (I-2a) ).

[Adhesive resin (I-2a)] The aforementioned adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group.

The aforementioned unsaturated group-containing compound is a compound having the following group: in addition to the aforementioned energy ray polymerizable unsaturated group, it also has adhesiveness by reacting with the functional group in the adhesive resin (I-1a) Resin (I-1a) is the bonding base. Examples of the energy ray polymerizable unsaturated group include (meth)acrylic acid group, vinyl (ethylene group), allyl group (2-propenyl group), etc., and (meth)acrylic acid group is preferred. base. Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include: isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amino groups, and carboxyl groups or epoxy groups that can be bonded The hydroxyl and amino groups, etc.

Examples of the aforementioned unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, and the like.

Adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected .

In the adhesive composition (I-2), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) is preferably 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, particularly preferably 10% by mass to 90% by mass.

[Crosslinking agent] For example, in the case of using the same acrylic polymer as the adhesive resin (I-1a) having a structural unit derived from a functional group-containing monomer as the adhesive resin (I-2a), the adhesive composition ( I-2) may further contain a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned adhesive composition (I-2), the content of the crosslinking agent relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass To 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the adhesive composition (I-2) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 20 parts by mass, more preferably 0.03 parts by mass Parts to 10 parts by mass, more preferably 0.05 to 5 parts by mass.

[Other additives, solvents] The adhesive composition (I-2) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-2), the same compounds as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-2) may each be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of the other additives and the solvent in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected according to the types of the other additives and the solvent.

[Adhesive composition (I-3)] The adhesive composition (I-3) contains the adhesive resin (I-2a) and the energy ray curable compound as described above.

In the adhesive composition (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-3) is preferably 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass.

[Energy ray hardening compound] Examples of the aforementioned energy-ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy-ray polymerizable unsaturated group and can be cured by irradiation with energy rays, including The same compound as the energy ray curable compound contained in the adhesive composition (I-1). The aforementioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type, or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned adhesive composition (I-3), the content of the aforementioned energy ray curable compound relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 300 parts by mass, more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. Even if the adhesive composition (I-3) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-3), the content of the photopolymerization initiator is 100 parts by mass relative to the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable compound, preferably 0.01 to 20 parts by mass Parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[Other additives, solvents] The adhesive composition (I-3) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-3), the same compounds as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-3) may be only one type, or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of the other additives and the solvent in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected according to the types of the other additives and the solvent.

[Adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)] In the foregoing, the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) were mainly described, but the components described as the contained components may be the same. It is used for all adhesive compositions except for these three types of adhesive compositions (in this specification, referred to as "adhesive composition (I-1) to adhesive compositions other than adhesive composition (I-3)) ").

As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy-ray-curable adhesive composition, non-energy-ray-curable adhesives can also be cited Composition. Examples of non-energy-ray curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and esters. The adhesive composition (I-4) of a non-energy-ray-curable adhesive resin (I-1a) such as resin preferably contains an acrylic resin.

Adhesive compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain one or more crosslinking agents, and the content of the crosslinking agent can be set to The adhesive composition (I-1) mentioned above is the same.

[Adhesive composition (I-4)] As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same adhesive resins as the adhesive resin (I-1a) in the adhesive composition (I-1). Adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected .

In the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total mass of the adhesive composition (I-4) is preferably 5 to 99% by mass, more preferably It is 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass.

[Crosslinking agent] When using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-4) may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned adhesive composition (I-4), the content of the crosslinking agent relative to the content of the adhesive resin (I-1a) is 100 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.1 part by mass To 47 parts by mass, particularly preferably 0.3 to 44 parts by mass.

[Other additives, solvents] The adhesive composition (I-4) may contain other additives that do not correspond to any of the above-mentioned components within a range that does not impair the effects of the present invention. In addition, the adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). As the aforementioned other additives and solvents in the adhesive composition (I-4), the same compounds as the other additives and solvents in the adhesive composition (I-1) can be cited, respectively. The other additives and solvents contained in the adhesive composition (I-4) may be only one type, or two or more types, respectively. In the case of two or more types, the combination and ratio of these can be arbitrarily selected. The content of the other additives and the solvent in the adhesive composition (I-4) is not particularly limited, and may be appropriately selected according to the types of the other additives and the solvent.

When the film for forming a protective film described later is energy ray curable, the adhesive layer is preferably non-energy ray curable. The reason is that if the adhesive layer is energy ray curable, it cannot be suppressed that the adhesive layer is also cured at the same time when the film for forming a protective film is cured by energy ray irradiation. If the adhesive layer and the film for forming a protective film are cured at the same time, the cured product of the film for forming a protective film and the adhesive layer may stick to the interface of each other to the extent that they cannot be peeled off. In this case, it is difficult to peel off the cured product with the protective film forming film on the inner surface, that is, the semiconductor wafer with the protective film (that is, the semiconductor wafer with the protective film) from the antifouling sheet provided with the cured product of the adhesive layer. It becomes impossible to pick up semiconductor wafers with protective films normally. If the adhesive layer is non-energy-ray curable, such a problem can be reliably avoided, and the semiconductor wafer with the protective film can be picked up more easily.

The effect when the adhesive layer is non-energy-ray curable is described here, but even if the layer directly in contact with the protective film forming film in the antifouling sheet is a layer other than the adhesive layer, as long as the layer is Non-energy ray hardening also exerts the same effect.

[Method of manufacturing adhesive composition] Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4) and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than that can be obtained by blending the aforementioned adhesive and components other than the aforementioned adhesive if necessary, etc., to constitute each component of the adhesive composition. The order of addition when preparing each component is not particularly limited, and two or more components may be added at the same time. When using a solvent, you can mix the solvent with any compounding component other than the solvent and dilute the compounding component in advance for use, or you can use the solvent and these compounding components without pre-diluting any compounding component other than the solvent Mix to use. The method of mixing each component during compounding is not particularly limited, and can be appropriately selected from the following well-known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves Methods of mixing, etc. The temperature and time when adding and mixing each component are not particularly limited as long as they do not deteriorate each compounding component, and they may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

◎Film for forming protective film The aforementioned protective film formation film may be curable or non-curable. The film for forming a curable protective film may be either thermosetting or energy ray curability, and it may have both properties of thermosetting and energy ray curability. In this specification, the "non-curing property" means the property that it is not cured by any method such as heating and irradiating energy rays.

When the protective film forming film is thermally cured to form a protective film, unlike the case where it is cured by irradiating energy rays, even if the thickness of the protective film forming film is thick, it will be sufficiently cured by heating. It can form a protective film with high protective performance. In addition, by using a general heating method such as a heating oven, a plurality of protective film forming films can be heated together to thermally harden them. When the protective film formation film is cured by energy ray irradiation to form a protective film, unlike the case of thermal curing, the composite sheet for protective film formation does not need to have heat resistance and can be used for a wide range of protective film formation Composite film. In addition, it can be cured in a short time by irradiating energy rays. When the film for forming a protective film is used as a protective film without hardening, the hardening step can be omitted, and therefore, a semiconductor wafer with a protective film can be manufactured in a simplified step.

The aforementioned protective film formation film becomes a protective film in its original state without being cured, or becomes a protective film by curing. The protective film is used to protect the semiconductor wafer or the inner surface of the semiconductor wafer (in other words, the surface opposite to the electrode formation surface). The protective film formation film is soft and can be easily attached to an attachment object.

In the case where the aforementioned protective film formation film is non-curable, the protective film formation film is used to attach the protective film formation composite sheet to the semiconductor wafer at the stage when the operation is completed as described later, it is regarded as being formed by the protective film A protective film is formed with the film.

In this specification, even after the protective film forming film is cured, as long as the layered structure of the antifouling sheet and the cured product of the protective film forming film (for example, protective film) is maintained, the layered structure is called "protective film forming Composite film".

Regardless of whether the protective film formation film is curable or non-curable, and when it is curable, whether it is thermosetting or energy ray curable, the protective film formation film can consist of one layer (Single layer) can also be composed of two or more layers. When the film for protective film formation is composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

Regardless of whether the protective film formation film is curable or non-curable, and in the case of curability, regardless of whether it is thermosetting or energy ray curability, the thickness of the protective film formation film is relatively It is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm, and particularly preferably 5 μm to 60 μm. When the thickness of the film for forming a protective film is more than the aforementioned lower limit, a protective film with higher protective ability can be formed. When the thickness of the film for forming a protective film is not more than the aforementioned upper limit, excessive thickness can be avoided. Here, the "thickness of the protective film formation film" means the overall thickness of the protective film formation film. For example, the thickness of the protective film formation film composed of multiple layers means the entirety of the protective film formation film The total thickness of the layer.

[Composition for forming protective film] The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, the protective film formation film can be formed by coating the protective film formation composition on the surface to be formed of the protective film formation film, and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the protective film formation composition is usually the same as the ratio of the contents of the aforementioned components in the protective film formation film. The film for forming a thermosetting protective film can be formed using the composition for forming a thermosetting protective film, and the film for forming an energy ray curable protective film can be formed using the composition for forming an energy ray curable protective film, and it is non-curable protection. The film for film formation can be formed using the composition for non-curable protective film formation. In addition, in this specification, when the protective film forming film has two characteristics of thermosetting and energy ray curability, the contribution of the thermal curing of the protective film forming film to the formation of the protective film is greater than that of the energy ray curing. In the case of the contribution, the protective film formation film is regarded as a thermosetting film. Conversely, when the contribution of the energy ray hardening of the protective film formation film to the formation of the protective film is greater than the contribution of thermal hardening, the protective film formation film is regarded as an energy ray hardened film.

The coating of the composition for forming a protective film can be performed, for example, by the same method as in the case of coating the above-mentioned adhesive composition.

Regardless of whether the protective film forming film is curable or non-curable, and when it is curable, whether it is thermosetting or energy ray curable, the drying conditions of the protective film forming composition are not There is no particular limitation. However, when the composition for forming a protective film contains a solvent described later, it is preferable to heat and dry. In addition, the solvent-containing composition for forming a protective film is preferably heated and dried under the conditions of 70°C to 130°C and 10 seconds to 5 minutes, for example. However, the composition for forming a thermosetting protective film is preferably heat-dried so that the composition itself and the film for forming a thermosetting protective film formed from the composition are not thermally cured.

Hereinafter, the film for forming a thermosetting protective film, the film for forming an energy ray curable protective film, and the film for forming a non-curing protective film will be described in order.

○Film for forming thermosetting protective film Regarding the curing conditions when a film for forming a thermosetting protective film is attached to the inner surface of a semiconductor wafer and thermally cured to form a protective film, as long as the protective film has a degree of curing that can fully perform the function of the protective film , It is not particularly limited, and may be appropriately selected according to the type of film for forming a thermosetting protective film. For example, the heating temperature during thermal curing of the film for forming a thermosetting protective film is preferably 100°C to 200°C, more preferably 110°C to 180°C, and particularly preferably 120°C to 170°C. In addition, the heating time during thermal hardening is preferably 0.5 hour to 5 hours, more preferably 0.5 hour to 3 hours, and particularly preferably 1 hour to 2 hours.

As a preferable film for forming a thermosetting protective film, for example, a film containing a polymer component (A) and a thermosetting component (B) can be cited. The polymer component (A) is regarded as a component formed by the polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is a component that can undergo a hardening (polymerization) reaction using heat as a trigger of the reaction. In addition, in this specification, a polycondensation reaction is also included in the polymerization reaction.

[Composition for forming thermosetting protective film (III-1)] As a preferable composition for forming a thermosetting protective film, for example, a composition for forming a thermosetting protective film (III-1) containing the aforementioned polymer component (A) and thermosetting component (B) (this In the specification, it may be simply referred to as "composition (III-1)") and so on.

[Polymer component (A)] The polymer component (A) is a component for imparting film forming properties or flexibility to the film for forming a thermosetting protective film. The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

Examples of the polymer component (A) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like, and acrylic resins are preferred.

As the aforementioned acrylic resin in the polymer component (A), a known acrylic polymer can be cited. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or greater than the aforementioned lower limit, the shape stability of the film for forming a thermosetting protective film (stability with time during storage) is improved. When the weight average molecular weight of the acrylic resin is below the above upper limit, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, and it can be further suppressed for the formation of the adherend and the thermosetting protective film. Voids and the like are generated between the films. In addition, in this specification, the "weight average molecular weight" means a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin is more than the aforementioned lower limit, for example, the adhesion between the cured product of the protective film forming film and the antifouling sheet is suppressed, and the releasability of the antifouling sheet is moderately improved. When the Tg of the acrylic resin is equal to or lower than the aforementioned upper limit, the adhesive force between the film for forming a thermosetting protective film and its cured product and the adherend is improved.

Acrylic resin has m kinds of structural units (m is an integer of 2 or more). For the m kinds of monomers derived from these structural units, any one from 1 to m is assigned in sequence and a non-repeating number is assigned and named as "monomer". In the case of m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox formula shown below.

(式中，Tg為丙烯酸樹脂的玻璃轉移溫度；m為2以上之整數；Tg_k 為單體m之均聚物的玻璃轉移溫度；W_k 為丙烯酸樹脂中的由單體m衍生之構成單元m的質量分率，其中，W_k 滿足下述式)[Number 1]

(In the formula, Tg is the glass transition temperature of acrylic resin; m is an integer greater than 2; Tg _k is the glass transition temperature of the homopolymer of monomer m; W _k is the structural unit derived from monomer m in acrylic resin The mass fraction of m, where W _k satisfies the following formula)

(式中，m及W_k 與前述相同)[Number 2]

(In the formula, m and W _{k are the} same as above)

As the aforementioned Tg _k , the values described in the polymer materials/manuals or adhesive manuals can be used. For example, the methacrylate homopolymer Tg _k of 10 ℃, of a methyl methacrylate homopolymer Tg _k of 105 ℃, of 2-hydroxyethyl acrylate homopolymer Tg _k of -15 ℃.

Examples of acrylic resins include: one or two or more (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxy Copolymers of two or more monomers in methacrylamide, etc.

In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The terms similar to (meth)acrylic acid are also the same. For example, the concept of "(meth)acrylic acid group" includes both "acrylic acid group" and "methacrylic acid group", and "(meth)acrylate" The concept includes both "acrylate" and "methacrylate".

Examples of the (meth)acrylate constituting the acrylic resin include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate , N-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, (meth) )Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate Ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Alkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute one of the alkyl esters The alkyl group is a (meth)acrylic acid alkyl ester with a chain structure with carbon number of 1 to 18; (meth)acrylic acid cycloalkyl group such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. Esters; aralkyl (meth)acrylates such as benzyl (meth)acrylate; cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenoxy (meth)acrylate (Meth)acrylic acid cycloalkenyloxyalkyl esters such as ethyl ester; (meth)acrylimines; glycidyl (meth)acrylate and other glycidyl-containing (meth)acrylates; (meth) ) Hydroxymethyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Hydroxy-containing (meth)acrylates such as 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; N-methylaminoethyl (meth)acrylate containing substituted amino groups The (meth)acrylate and so on. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms.

The acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the aforementioned (meth)acrylate. Acrylic resin made by copolymerization of one or more monomers.

The monomer constituting the acrylic resin may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

The acrylic resin may also have functional groups such as vinyl groups, (meth)acrylic groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds. The aforementioned functional group of the acrylic resin may be bonded to other compounds via the crosslinking agent (F) described later, or may be directly bonded to other compounds without the crosslinking agent (F). When the acrylic resin is bonded to another compound via the aforementioned functional group, the reliability of the package obtained by using the composite sheet for forming a protective film tends to be improved.

In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter, simply referred to as "thermoplastic resin" in some cases) may be used alone instead of an acrylic resin, or may be used in combination with an acrylic resin. By using the aforementioned thermoplastic resin, the peelability of the protective film from the supporting sheet may be improved, or the film for forming a thermosetting protective film may easily follow the uneven surface of the adherend, which can further suppress the adhesion to the adherend and heat. There are voids between the films for forming the curable protective film.

The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

As said thermoplastic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

The aforementioned thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination and ratio of these resins may be Free to choose.

In the composition (III-1), regardless of the type of the polymer component (A), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the thermosetting protective film is formed) The ratio of the content of the polymer component (A) in the film to the total mass of the film for forming a thermosetting protective film) is preferably 5 to 85% by mass, more preferably 5 to 80% by mass For example, it can be any of 5 mass% to 65% by mass, 5 mass% to 50 mass%, 5 mass% to 35% by mass, 10 mass% to 35% by mass, and 15 mass% to 35% by mass.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains such components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing polymer Material component (A) and thermosetting component (B).

[Thermosetting component (B)] The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film. The composition (III-1) and the thermosetting component (B) contained in the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, these The combination and ratio can be selected arbitrarily.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, polyimide-based resins, and unsaturated polyester resins, and epoxy-based thermosetting resins are preferred.

[Epoxy-based thermosetting resin] The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2). The epoxy-based thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be selected arbitrarily.

・Epoxy resin (B1) As the epoxy resin (B1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy Resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins and other epoxy resins with more than two functions Compound.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a semiconductor wafer with a protective film obtained by using a composite sheet for forming a protective film is improved.

As an epoxy resin having an unsaturated hydrocarbon group, for example, a compound obtained by converting a part of epoxy groups of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group can be cited. Such a compound is obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group. In addition, as an epoxy resin having an unsaturated hydrocarbon group, for example, a compound having a group having an unsaturated hydrocarbon group directly bonded to an aromatic ring constituting the epoxy resin or the like can be cited. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acrylic, The (meth)acrylamido group, etc., is preferably an acrylamido group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but in terms of the curability of the thermosetting protective film forming film, and the strength and heat resistance of the protective film, it is preferably 300 to 30,000, and more It is preferably 300 to 10,000, particularly preferably 300 to 3,000. The epoxy equivalent of the epoxy resin (B1) is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 950 g/eq.

The epoxy resin (B1) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, these combination and ratio can be selected arbitrarily.

・Thermal hardener (B2) The thermal hardener (B2) functions as a hardener for the epoxy resin (B1). As a thermosetting agent (B2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned, preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride The formed group is more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. Phenolic resin, etc. Among the thermosetting agents (B2), examples of the amine-based curing agent having an amine group include dicyandiamide.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group. As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a compound having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin Based on the compound and so on. The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

In the thermosetting agent (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30,000, and more It is preferably 400 to 10,000, particularly preferably 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited. For example, it is preferably 60 to 500.

A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, these combination and ratio can be selected arbitrarily.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) relative to 100 parts by mass of the epoxy resin (B1), preferably 0.1 to 500 parts by mass , More preferably 1 part by mass to 200 parts by mass, for example, can be any of 1 part by mass to 100 parts by mass, 1 part by mass to 50 parts by mass, 1 part by mass to 25 parts by mass, and 1 part by mass to 10 parts by mass . When the said content of a thermosetting agent (B2) is more than the said lower limit, the film for thermosetting protective film formation becomes easy to harden. When the aforementioned content of the thermosetting agent (B2) is below the aforementioned upper limit, the moisture absorption rate of the thermosetting protective film formation film is reduced, and the reliability of the package obtained using the protective film formation composite sheet is further improved.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymerization The content of the material component (A) is 100 parts by mass, preferably 20 parts by mass to 500 parts by mass, more preferably 25 parts by mass to 300 parts by mass, still more preferably 30 parts by mass to 150 parts by mass, for example, 35 parts by mass Any one of parts to 100 parts by mass, and 40 parts to 80 parts by mass. When the aforementioned content of the thermosetting component (B) is in this range, for example, the adhesive force of the cured product of the protective film forming film and the antifouling sheet is suppressed, and the peelability of the antifouling sheet is improved.

[Hardening accelerator (C)] The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1). As a preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (one or more Phosphine in which hydrogen atoms are replaced by organic groups); tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

The composition (III-1) and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

In the case of using the curing accelerator (C), the content of the curing accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the content of the thermosetting component (B) 100 Parts by mass, preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 7 parts by mass. When the aforementioned content of the hardening accelerator (C) is more than the aforementioned lower limit, the effect of using the hardening accelerator (C) can be more remarkably obtained. Since the content of the hardening accelerator (C) is below the aforementioned upper limit, for example, the high-polar hardening accelerator (C) is prevented from being thermally curable in the film for forming a thermosetting protective film under high temperature and high humidity conditions. The adhesion interface side between the film for film formation and the adherend moves to increase the effect of segregation. As a result, the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for forming a protective film is further improved.

[Filling material (D)] The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). When the thermosetting protective film forming film contains the filler (D), the protective film obtained by curing the thermosetting protective film forming film can easily adjust the thermal expansion coefficient so that the thermal expansion coefficient is relative to the object to be formed of the protective film Most preferably, the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for forming a protective film is further improved. In addition, when the film for forming a thermosetting protective film contains the filler (D), the moisture absorption rate of the protective film can also be reduced, or the heat dissipation can be improved.

The filling material (D) can be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material. As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by spheronizing these inorganic fillers. Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler material is preferably silica or alumina, and more preferably silica.

The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

When the filler (D) is used, in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, for forming a thermosetting protective film) The ratio of the content of the filler (D) in the film to the total mass of the film for forming a thermosetting protective film) is preferably 5 mass% to 80 mass%, more preferably 10 mass% to 70 mass%, for example, It is any of 20% by mass to 65% by mass, 30% by mass to 65% by mass, and 40% by mass to 65% by mass. With the aforementioned ratio in this range, it is easier to adjust the thermal expansion coefficient of the aforementioned protective film.

[Coupling agent (E)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the film for forming a thermosetting protective film to the adherend can be improved. In addition, by using the coupling agent (E), the protective film formed from the film for forming a thermosetting protective film does not impair heat resistance and improves water resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional group possessed by the polymer component (A) and the thermosetting component (B), and more preferably a silane coupling agent. As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triethoxysilane, imidazole silane, etc.

The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the polymer component (A) and the thermosetting component ( The total content of B) is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (E) is above the aforementioned lower limit, the following effects brought about by the use of the coupling agent (E) can be obtained more significantly: the dispersibility of the filler (D) in the resin is improved, Or the adhesion between the film for forming a thermosetting protective film and the adherend is improved. When the aforementioned content of the coupling agent (E) is below the aforementioned upper limit, the generation of outgassing can be further suppressed.

[Crosslinking agent (F)] When using the above-mentioned acrylic resin with functional groups such as vinyl, (meth)acrylic acid group, amino group, hydroxyl group, carboxyl group, isocyanate group, etc., which can be bonded with other compounds, as the polymer component (A), the composition The compound (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component used to bond the aforementioned functional groups in the polymer component (A) to other compounds for cross-linking. By cross-linking in this way, the film for forming a thermosetting protective film can be adjusted The initial adhesion and cohesion.

Examples of the crosslinking agent (F) include: organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurates and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound with a low content of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. A reactant of molecular active hydrogen compounds. As an example of the said adduct, the xylylene diisocyanate adduct of trimethylolpropane etc. mentioned later can be mentioned. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate Diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophor Ketone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate is added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Compounds of any one or more of isocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinemethamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinylmethamine) triethylene Based on melamine and so on.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced into the In the film for forming a thermosetting protective film.

The composition (III-1) and the crosslinking agent (F) contained in the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

In the case of using the crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III-1) is 100 parts by mass relative to the content of the polymer component (A), preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 0.5 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (F) is more than the aforementioned lower limit, the effect of using the cross-linking agent (F) can be more remarkably obtained. When the aforementioned content of the cross-linking agent (F) is below the aforementioned upper limit, the excessive use of the cross-linking agent (F) can be suppressed.

[Energy ray curable resin (G)] The composition (III-1) and the film for forming a thermosetting protective film may contain an energy ray-curable resin (G). Since the film for forming a thermosetting protective film contains energy-ray-curable resin (G), its characteristics can be changed by energy-ray irradiation.

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound. Examples of the aforementioned energy ray curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylates and other (meth)acrylates containing chain aliphatic skeletons; dicyclopentyl di(meth)acrylates and other (meth)acrylates containing cyclic aliphatic skeletons; polyethylene glycol Di(meth)acrylate and other polyalkylene glycol (meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modified (former Base) acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligomer, etc.

The weight average molecular weight of the aforementioned energy ray curable compound is preferably 100 to 30,000, more preferably 300 to 10,000.

The aforementioned energy ray curable compound used for polymerization may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

The composition (III-1) and the energy ray curable resin (G) contained in the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio of can be selected arbitrarily.

In the case of using the energy ray curable resin (G), the ratio of the content of the energy ray curable resin (G) to the total mass of the composition (III-1) in the composition (III-1) is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 85% by mass.

[Photopolymerization initiator (H)] When the composition (III-1) and the film for forming a thermosetting protective film contain energy ray curable resin (G), in order to efficiently polymerize the energy ray curable resin (G), it may also contain Photopolymerization initiator (H).

Examples of the photopolymerization initiator (H) in the composition (III-1) include the same compounds as the photopolymerization initiator contained in the above-mentioned adhesive composition (I-1).

The photopolymerization initiator (H) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types. In the case of two or more types, these The combination and ratio of can be selected arbitrarily.

In the case of using the photopolymerization initiator (H), in the composition (III-1), the content of the photopolymerization initiator (H) relative to the content of the energy ray curable resin (G) is 100 parts by mass. It is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, and particularly preferably from 2 parts by mass to 5 parts by mass.

[Colorant (I)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coloring agent (I). As a coloring agent (I), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, an organic type dye, etc. are mentioned, for example.

Examples of the aforementioned organic pigments and organic dyes include: ammonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, squalilium-based pigments, and azulenium-based pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene lactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol Pigments, methine azo pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, etc.

Examples of the aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) based pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) based pigments, etc.

The coloring agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily.

When using the coloring agent (I), the content of the coloring agent (I) in the film for forming a thermosetting protective film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film to adjust the light transmittance of the film for forming a thermosetting protective film, it is possible to adjust the performance of the film for forming a thermosetting protective film. The visibility of printing in the case of laser printing. In addition, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film, it is also possible to improve the design of the protective film or make it difficult to see the grinding marks on the inner surface of the semiconductor wafer. Considering these aspects, the ratio of the content of the colorant (I) in the composition (III-1) to the total content of all components other than the solvent (that is, the coloring agent in the film for forming a thermosetting protective film The ratio of the content of (I) to the total mass of the film for forming a thermosetting protective film) is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 7.5% by mass, and particularly preferably 0.01% by mass to 5 mass%. When the aforementioned ratio is greater than or equal to the aforementioned lower limit, the effect brought about by the use of the colorant (I) can be more remarkably obtained. When the aforementioned ratio is equal to or less than the aforementioned upper limit, it is possible to suppress an excessive decrease in the light transmittance of the film for forming a thermosetting protective film.

[General additives (J)] The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention. The general additives (J) can be well-known compounds, which can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general additives (J) include, for example, plasticizers, antistatic agents, antioxidants, and getters. (gettering agent) and so on.

The general additives (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination of these and The ratio can be chosen arbitrarily. The content of the general additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent] The composition (III-1) preferably further contains a solvent. The solvent-containing composition (III-1) has good operability. The aforementioned solvent is not particularly limited, and preferable examples of the aforementioned solvent include the same compounds as the solvent contained in the aforementioned adhesive composition (I-1). The solvent contained in the composition (III-1) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like in terms of allowing the components contained in the composition (III-1) to be mixed more uniformly.

The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

[Manufacturing method of composition for forming thermosetting protective film] The composition for forming a thermosetting protective film, such as the composition (III-1), is obtained by blending each component that constitutes the composition. The composition for forming a thermosetting protective film can be manufactured by the same method as that of the adhesive composition described above, except for the point that the types of the compounding components are different, for example.

○Film for forming energy ray curable protective film Regarding the curing conditions when the energy ray curable protective film forming film is attached to the inner surface of a semiconductor wafer and the energy ray is cured to form a protective film, as long as the protective film is sufficient The degree of curing to achieve the function of the protective film is not particularly limited, and may be appropriately selected according to the type of the energy ray curable protective film forming film. For example, the illuminance of the energy ray when the energy ray of the film for forming an energy ray curable protective film is cured is preferably 60 mW/cm ² to 320 ^{mW/cm 2} . In addition, the light amount of the energy ray during curing is preferably 100 mW/cm ² to 1000 mJ/cm ² .

Examples of the film for forming an energy ray curable protective film include a film containing an energy ray curable component (a), and a film containing an energy ray curable component (a) and a filler is preferred. In the film for forming an energy ray curable protective film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably has uncured and adhesiveness.

[Composition for forming energy ray curable protective film (IV-1)] As a preferable composition for forming an energy ray curable protective film, for example, a composition (IV-1) for forming an energy ray curable protective film containing the aforementioned energy ray curable component (a) (in this specification, there is Sometimes it is simply referred to as "Composition (IV-1)") and so on.

[Energy ray hardening component (a)] The energy-ray curable component (a) is a component that is cured by irradiating energy rays. The component is used to impart film-forming properties or flexibility to the energy-ray-curable protective film forming film, and to form a hard surface after curing. Protective film. Examples of the energy ray curable component (a) include: a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000 (a2). The aforementioned polymer (a1) may be cross-linked at least in part by a cross-linking agent, or may be an uncross-linked product.

[Polymer (a1) having an energy-ray curable base and a weight average molecular weight of 80,000 to 2,000,000] As the polymer (a1) having an energy-ray curable group and having a weight average molecular weight of 80,000 to 2,000,000, for example, acrylic resin (a1-1) can be cited. The acrylic resin (a1-1) is made of acrylic polymer (a11) and An energy ray-curable compound (a12) is formed by reacting, the acrylic polymer (a11) has a functional group that can react with a group possessed by other compounds, and the energy-beam-curable compound (a12) has a functional group that reacts with the aforementioned functional group Energy-ray-curable groups such as energy-ray-curable double bonds.

Examples of the aforementioned functional groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. Group), epoxy group and the like. However, in terms of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer, the aforementioned functional group is preferably a group other than a carboxyl group. Among these, the aforementioned functional group is preferably a hydroxyl group.

・Acrylic polymer with functional group (a11) As the acrylic polymer (a11) having the aforementioned functional group, for example, a copolymer obtained by copolymerizing an acrylic monomer having the aforementioned functional group and an acrylic monomer not having the aforementioned functional group may be used; In addition to the monomer, a copolymer formed by copolymerizing monomers other than acrylic monomers (non-acrylic monomers). In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer. Regarding the polymerization method, a known method may also be adopted.

Examples of the acrylic monomer having the aforementioned functional group include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amine group-containing monomers, epoxy group-containing monomers, and the like.

Examples of the aforementioned hydroxyl-containing monomer include the same monomers as the hydroxyl-containing monomer constituting the adhesive resin (I-1a) contained in the adhesive composition (I-1) described above.

Examples of the aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); the anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (formula Group) carboxyalkyl acrylate and the like.

The acrylic monomer having the aforementioned functional group is preferably a hydroxyl-containing monomer.

The acrylic monomer having the aforementioned functional group constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

As an acrylic monomer that does not have the aforementioned functional group, for example, a (meth)acrylate (meth)acrylate that composes the acrylic resin in the above-mentioned polymer component (A) (the alkyl group that composes the alkyl ester has a carbon number of 1 to 18) The chain structure of (meth)acrylic acid alkyl ester) is the same as the acrylic monomer.

In addition, examples of acrylic monomers that do not have the aforementioned functional group include: methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate , (Meth) ethoxy ethyl acrylate and other (meth) acrylates containing alkoxy alkyl groups; those containing aryl (meth) acrylates such as phenyl (meth) acrylate, etc., which have aromatic groups (Meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N-di (Meth)acrylates with non-crosslinkable tertiary amino groups, such as methylaminopropyl.

The acrylic monomer which does not have the said functional group which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types. When it is 2 or more types, these combination and ratio can be selected arbitrarily.

Examples of the aforementioned non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like. The aforementioned non-acrylic monomer constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of constituent units derived from the acrylic monomer having the aforementioned functional group to the total amount of constituent units constituting the acrylic polymer (a11) is preferably 0.1 mass % To 50% by mass, more preferably 1% to 40% by mass, particularly preferably 3% to 30% by mass. When the aforementioned ratio is in this range, the content of the energy-ray-curable group in the acrylic resin (a1-1) obtained by the copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy-ray-curable compound (a12) can be easily The ground is adjusted to a better range for the degree of hardening of the protective film.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (that is, the acrylic resin (a1-1) in the film for forming an energy ray curable protective film The ratio of the content of) to the total mass of the aforementioned film) is preferably 1% to 70% by mass, more preferably 5% to 60% by mass, and particularly preferably 10% to 50% by mass.

・Energy ray curable compound (a12) The aforementioned energy ray curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a function that can be combined with the aforementioned acrylic polymer (a11) The group reacting with the group preferably has an isocyanate group as the aforementioned group. When the energy ray curable compound (a12) has an isocyanate group as the aforementioned group, for example, the isocyanate group and the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group easily react.

The number of energy ray curable groups contained in the energy ray curable compound (a12) per molecule is not particularly limited. For example, it can be appropriately selected in consideration of physical properties such as shrinkage rate required for the target protective film. For example, the aforementioned energy-ray-curable compound (a12) preferably has 1 to 5 of the aforementioned energy-ray-curable group in one molecule, and more preferably has 1 to 3.

Examples of the energy ray curable compound (a12) include: 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylic acid Isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate Acrylic monoisocyanate compound obtained; Acrylic monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate. Among these, the aforementioned energy ray curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The aforementioned energy ray curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferable It is 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in this range, the adhesive force of the protective film becomes greater. In addition, when the aforementioned energy ray curable compound (a12) is a monofunctional (having one aforementioned group in a molecule) compound, the upper limit of the aforementioned content ratio becomes 100 mol%, but the aforementioned energy ray curable compound (a12) When the curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol%.

The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000. Here, the so-called "weight average molecular weight" is as described above.

When at least a part of the aforementioned polymer (a1) is crosslinked by a crosslinking agent, the aforementioned polymer (a1) may be any monomer that does not correspond to the aforementioned acrylic polymer (a11) And the monomer having a group that reacts with the crosslinking agent is polymerized and crosslinked in the group that reacts with the crosslinking agent, it may also be derived from the energy ray curable compound (a12) and the aforementioned functional group. The reaction base is cross-linked.

The aforementioned polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be selected arbitrarily.

[Compound (a2) having an energy-ray curable group and having a molecular weight of 100 to 80,000] As the aforementioned energy-ray-curable group in the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000, a group containing an energy-ray-curable double bond may be mentioned, and as a preferable group, (former) Base) acryloyl, vinyl and the like.

The aforementioned compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, and phenol resins having energy ray curable groups. Wait.

Among the aforementioned compounds (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and preferably acrylate-based compounds having a (meth)acryloyl group. Examples of the acrylate-based compound include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxy Bisphenol A bis(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) )Acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy) phenyl] 茀, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1 , 10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate ) Acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, Neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis(meth)acryloxypropane and other bifunctional (methyl) ) Acrylate; Tris(2-(meth)acryloyloxyethyl) isocyanurate, ε-caprolactone modified isocyanurate tris-(2-(meth)acryloyloxyethyl) Base) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(methyl) ) Acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. (Meth)acrylate; (meth)acrylate urethane oligomers and other multifunctional (meth)acrylate oligomers.

Among the aforementioned compounds (a2), as an epoxy resin having an energy ray curable group and a phenol resin having an energy ray curable group, for example, the one described in paragraph 0043 of "JP 2013-194102 A" can be used. Resin. Such resin is also equivalent to the resin constituting the thermosetting component described later, but is regarded as the aforementioned compound (a2) in the present invention.

The weight average molecular weight of the aforementioned compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

The aforementioned compound (a2) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be one type or two or more types. In the case of two or more types, a combination of these And the ratio can be chosen arbitrarily.

[Polymer without energy ray curable base (b)] When the composition (IV-1) and the film for forming an energy ray curable protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain the non-energy ray curable component (a). Base polymer (b). The aforementioned polymer (b) may be cross-linked at least partially by a cross-linking agent, or may be an uncross-linked product.

Examples of the polymer (b) that does not have an energy-ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, acrylic urethane resins, etc. . Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)" in some cases).

The acrylic polymer (b-1) may be a well-known polymer, for example, it may be a homopolymer of one type of acrylic monomer, or a copolymer of two or more types of acrylic monomers, or one or two types. A copolymer of the above acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth) glycidyl groups. Acrylate, hydroxyl-containing (meth)acrylate, substituted amino group-containing (meth)acrylate, etc. Here, the so-called "substituted amino group" is as described above.

As the aforementioned (meth)acrylic acid alkyl ester, for example, the acrylic monomer that does not have the aforementioned functional group that constitutes the acrylic polymer (a11) explained above (the alkyl group that constitutes the alkyl ester has a carbon number of 1 to The chain structure of 18 (meth)acrylic acid alkyl ester, etc.) is the same compound.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth) ) Aralkyl (meth)acrylates such as benzyl acrylate; cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenoxyethyl (meth)acrylate, etc. ( Cycloalkenyloxyalkyl meth)acrylate and the like.

As said glycidyl group-containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example. As the aforementioned hydroxyl group-containing (meth)acrylates, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the aforementioned substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate and the like.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.

As a polymer (b) that is at least partially cross-linked by a cross-linking agent and does not have the aforementioned energy ray curable group, for example, a reactive functional group in the aforementioned polymer (b) reacts with a cross-linking agent. polymer. The above-mentioned reactive functional group may be appropriately selected according to the kind of crosslinking agent, etc., and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amino group, etc. can be mentioned. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent is an epoxy-based compound, as the aforementioned reactive functional group, a carboxyl group, an amino group, an amide group, etc. can be cited. Among these, the one having high reactivity with the epoxy group is preferred. carboxyl. However, in terms of preventing corrosion of the semiconductor wafer or the circuit of the semiconductor wafer, the aforementioned reactive functional group is preferably a group other than a carboxyl group.

As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) are used having the aforementioned A monomer with a reactive functional group is sufficient. For the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate may be mentioned. In addition to this, the above-mentioned A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms of the aforementioned acrylic monomer or non-acrylic monomer is substituted with the aforementioned reactive functional group.

In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of constituent units derived from a monomer having a reactive functional group relative to the total amount of constituent units constituting the polymer (b) It is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass. When the aforementioned ratio is in such a range, the degree of crosslinking in the aforementioned polymer (b) becomes a more preferable range.

In terms of better film-forming properties of the composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) that does not have an energy-ray curable group is preferably 10,000 to 2,000,000, more preferably 100,000 To 1500000. Here, the so-called "weight average molecular weight" is as described above.

The composition (IV-1) and the polymer (b) that does not have an energy ray curable group contained in the film for forming an energy ray curable protective film may be only one type, or two or more types, or two types In the above case, the combination and ratio of these can be arbitrarily selected.

As the composition (IV-1), a composition containing either or both of the aforementioned polymer (a1) and aforementioned compound (a2) can be cited. In addition, when the composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy-ray curable group, and in this case, it is also preferable to further contain The foregoing (a1). In addition, the composition (IV-1) may not contain the above-mentioned compound (a2), and may also contain the above-mentioned polymer (a1) and a polymer (b) which does not have an energy-ray curable group.

When the composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and the aforementioned polymer (b) without an energy-ray curable group, in the composition (IV-1), the aforementioned compound The content of (a2) is 100 parts by mass relative to the total content of the aforementioned polymer (a1) and polymer (b) without energy ray curable groups, preferably 10 parts by mass to 400 parts by mass, more preferably 30 parts by mass Parts to 350 parts by mass.

In the composition (IV-1), the ratio of the total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group to the total content of components other than the solvent (that is, The ratio of the total content of the aforementioned energy-ray-curable component (a) and the polymer (b) not having an energy-ray-curable group to the total mass of the aforementioned film in the film for forming an energy-ray curable protective film is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass. When the aforementioned ratio of the content of the energy ray curable component is in this range, the energy ray curability of the film for forming an energy ray curable protective film becomes better.

In the composition (IV-1), in addition to the aforementioned energy ray curable component, it may also contain a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a coloring agent, and the like according to the purpose. One or more than two types in the group consisting of general additives.

As the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives in the composition (IV-1), there may be mentioned those in the composition (III-1). The thermosetting component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), coloring agent (I) and general additives (J) are the same Compound.

For example, by using the composition (IV-1) containing the aforementioned energy ray curable component and thermosetting component, the formed film for forming an energy ray curable protective film increases the adhesive force to the adherend by heating , The strength of the protective film formed from the film for forming the energy ray curable protective film is also improved. In addition, by using the composition (IV-1) containing the aforementioned energy ray curable component and coloring agent, the formed energy ray curable protective film formation film exhibits the same characteristics as the thermosetting protective film described above. The same effect is achieved when the film contains the coloring agent (I).

In the composition (IV-1), the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives may be used singly, or two or more of them may be used in combination. When two or more types are used in combination, the combination and ratio of these can be arbitrarily selected.

The content of the aforementioned thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent, and general additives in the composition (IV-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

In terms of improving the operability of the composition (IV-1) by dilution, the composition (IV-1) preferably further contains a solvent. Examples of the solvent contained in the composition (IV-1) include the same solvents as the solvent in the composition (III-1). The solvent contained in the composition (IV-1) may be only one type or two or more types. The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

[Method for manufacturing composition for forming energy ray curable protective film] A composition for forming an energy ray curable protective film, such as composition (IV-1), is obtained by blending each component that constitutes the composition. The composition for forming an energy ray curable protective film is manufactured by the same method as that of the adhesive composition described above, except for the difference in the types of compounding components, for example.

○Film for forming non-curable protective film As a preferable film for forming a non-curable protective film, for example, a film containing a thermoplastic resin and a filler can be cited.

[Composition for forming non-curable protective film (V-1)] As a preferable composition for forming a non-curable protective film, for example, a composition for forming a non-curable protective film containing the aforementioned thermoplastic resin and filler (V-1) (in this specification, sometimes simply referred to as " Composition (V-1)”) etc.

[Thermoplastic resin] The aforementioned thermoplastic resin is not particularly limited. As the aforementioned thermoplastic resins, more specifically, for example, acrylic resins, polyesters, polyurethanes, phenoxy resins, and polybutylene resins listed as components of the above-mentioned composition (III-1) can be cited. Non-curable resins such as olefin, polybutadiene, polystyrene, etc. are the same resins.

The aforementioned thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be only one type or two or more types. In the case of two or more types, the combination and ratio of these resins may be Free to choose.

In the composition (V-1), the ratio of the content of the thermoplastic resin to the total content of components other than the solvent (that is, the content of the thermoplastic resin in the film for forming a non-curable protective film relative to the non-curable protective film The ratio of the total mass of the film for film formation) is preferably 25% by mass to 75% by mass.

[Filler] The film for forming a non-curable protective film containing a filler exerts the same effect as the film for forming a thermosetting protective film containing a filler (D).

Examples of the filler contained in the composition (V-1) and the film for forming a non-curable protective film include the filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film The same compound.

The filler material contained in the composition (V-1) and the film for forming a non-curable protective film may be only one type or two or more types. In the case of two or more types, the combination and ratio of these may be arbitrary select.

In the composition (V-1), the ratio of the content of the filler to the total content of all components other than the solvent (that is, the content of the filler in the film for forming a non-curing protective film relative to the non-curing protective film The ratio of the total mass of the film for formation) is preferably 25% by mass to 75% by mass. When the aforementioned ratio is in this range, it is easier to adjust the thermal expansion coefficient of the protective film (in other words, the film for forming a non-curable protective film) as in the case of using the composition (III-1).

In the composition (V-1), in addition to the aforementioned thermoplastic resin and filler, other components may be contained according to the purpose. The aforementioned other components are not particularly limited, and can be arbitrarily selected according to the purpose. For example, by using the composition (V-1) containing the aforementioned thermoplastic resin and coloring agent, the formed non-curable protective film forming film (in other words, the protective film) exhibits the same thermosetting protective film as described above The same effect is obtained when the film for formation contains the coloring agent (I).

In the composition (V-1), the aforementioned other components may be used alone or in combination of two or more types. When two or more types are used in combination, the combination and ratio of these may be arbitrarily selected.

The content of the aforementioned other components in the composition (V-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

In terms of improving the operability of the composition (V-1) by dilution, the composition (V-1) preferably further contains a solvent. Examples of the solvent contained in the composition (V-1) include the same compounds as the solvent in the above-mentioned composition (III-1). The solvent contained in the composition (V-1) may be only one type or two or more types. The content of the solvent in the composition (V-1) is not particularly limited, and may be appropriately selected according to the types of components other than the solvent, for example.

[Method for manufacturing composition for forming non-curable protective film] The composition for forming a non-curable protective film, such as the composition (V-1), is obtained by blending each component that constitutes the composition. The composition for forming a non-curable protective film, for example, can be manufactured by the same method as the adhesive composition described above, except for the difference in the types of compounding components.

As a preferable example of the composite sheet for forming a protective film of the present embodiment, the following composite sheet for forming a protective film can be cited: it is used for attaching to the inner surface of a semiconductor wafer to form a protective film on the inner surface; The composite sheet for forming a protective film includes an antifouling sheet and a film for forming a protective film formed on one side of the antifouling sheet; the film for forming the protective film can form the protective film; the composite sheet for forming a protective film is relative to The maximum width of the composite sheet for forming a protective film in a direction parallel to the attachment surface of the semiconductor wafer is 155mm to 194mm, 205mm to 250mm, 305mm to 350mm, or 455mm to 500mm; the aforementioned antifouling sheet It is provided with a substrate and an adhesive layer formed on one surface of the substrate, and the composite sheet for forming a protective film is composed of the substrate, the adhesive layer, and the film for forming a protective film in sequence; the substrate is selected One or two or more of the group consisting of polyethylene, polypropylene and polyethylene terephthalate are used as constituent materials; the aforementioned adhesive layer is energy ray hardenable or non-energy ray hardenable; energy ray The aforementioned curable adhesive layer is formed by using an adhesive composition (I-2) containing an energy-ray curable adhesive resin (I-2a) and a cross-linking agent; the aforementioned adhesive resin (I-2a) is The aforementioned functional group in the adhesive resin (I-1a) having a structural unit derived from alkyl (meth)acrylate and a structural unit derived from a functional group-containing monomer is combined with energy ray polymerizable unsaturated The above-mentioned crosslinking agent reacts with the above-mentioned functional group to cross-link the above-mentioned adhesive resin (I-2a) with each other. In the above-mentioned adhesive composition (I-2), the above-mentioned cross-linking The content of the linking agent is 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a); the non-energy-ray curable adhesive layer contains adhesive resin (I-1a) (Having a structural unit derived from alkyl (meth)acrylate and a structural unit derived from a functional group-containing monomer) and a cross-linking agent of the adhesive composition (I-4), the aforementioned cross-linking agent and The functional groups react to crosslink the adhesive resins (I-1a) with each other. In the adhesive composition (I-4), the content of the crosslinking agent is relative to the content of the adhesive resin (I-1a) 100 parts by mass is 0.1 parts by mass to 47 parts by mass; make a test piece of the aforementioned antifouling sheet with a width of 15mm, and perform the following tensile test, that is, under the temperature condition of 18°C to 28°C, the initial chuck When the interval is set to 100mm, and the test piece is stretched at a speed of 200mm/min in a direction parallel to the surface of the test piece, the test piece can be stretched by 15% or more, and the test piece is stretched by 10% The tensile strength is 4.0N/15mm or more.

As another preferable example of the composite sheet for forming a protective film of this embodiment, the following composite sheet for forming a protective film can be cited: it is used for attaching to the inner surface of a semiconductor wafer to form a protective film on the aforementioned inner surface; The composite sheet for forming a protective film includes an antifouling sheet and a film for forming a protective film formed on one side of the antifouling sheet; the film for forming a protective film can form the protective film; the opposite of the composite sheet for forming a protective film The maximum width of the composite sheet for forming a protective film in a direction parallel to the attaching surface of the semiconductor wafer is 155mm to 194mm, 205mm to 250mm, 305mm to 350mm, or 455mm to 500mm; the aforementioned antifouling The sheet includes a substrate and an adhesive layer formed on one surface of the substrate. The composite sheet for forming a protective film is composed of the substrate, the adhesive layer, and the film for forming a protective film in sequence; the substrate is composed of One or two or more selected from the group consisting of polyethylene, polypropylene and polyethylene terephthalate as constituent materials; the aforementioned adhesive layer is energy ray hardenable or non-energy ray hardenable; energy; The aforementioned adhesive layer of linear curability is formed by using an adhesive composition (I-2) containing an energy-curable adhesive resin (I-2a) and a cross-linking agent. The aforementioned adhesive resin (I-2a) The aforementioned functional group in the adhesive resin (I-1a) having a structural unit derived from alkyl (meth)acrylate and a structural unit derived from a functional group-containing monomer is combined with energy ray polymerizable It is obtained by reacting an unsaturated group-containing compound with an unsaturated group, and the aforementioned crosslinking agent reacts with the aforementioned functional group to crosslink the aforementioned adhesive resins (I-2a) with each other. In the aforementioned adhesive composition (I-2), The content of the crosslinking agent is 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a); the non-energy-ray curable adhesive layer is made of an adhesive resin (I- 1a) (Having structural units derived from alkyl (meth)acrylate and structural units derived from functional group-containing monomers) and a cross-linking agent to form an adhesive composition (I-4), the aforementioned cross-linking The agent reacts with the functional group to cross-link the adhesive resin (I-1a) with each other. In the adhesive composition (I-4), the content of the cross-linking agent is relative to the adhesive resin (I-1a) The content of 100 parts by mass is 0.1 parts by mass to 47 parts by mass; the aforementioned protective film forming film contains polymer component (A), epoxy resin (B1) and thermosetting agent (B2), and is thermosetting, the aforementioned protective film In the film for forming, the content of the thermosetting agent (B2) is 1 part by mass to 25 parts by mass relative to 100 parts by mass of the content of the epoxy resin (B1). In the film for forming a protective film, the epoxy resin ( The total content of B1) and thermosetting agent (B2) is 35 parts by mass to 100 parts by mass relative to 100 parts by mass of the polymer component (A); a test piece of the aforementioned antifouling sheet with a width of 15 mm is made, and the following is performed The tensile test, that is, at 18 Under the temperature condition of ℃ to 28℃, the initial chuck spacing is set to 100mm, and the test piece can be stretched at a speed of 200mm/min in a direction parallel to the surface of the test piece. The tensile strength when elongation is 15% or more, and the aforementioned test piece is extended by 10% is 4.0N/15mm or more.

◇Manufacturing method of composite sheet for forming protective film The aforementioned composite sheet for forming a protective film can be manufactured by laminating each of the above-mentioned layers so as to have a corresponding positional relationship, and adjusting the shape of a part or all of the layers as necessary. The formation method of each layer is as described above.

For example, in the case of laminating an adhesive layer on a substrate when manufacturing an antifouling sheet, it is only necessary to apply the above-mentioned adhesive composition on the substrate and dry it if necessary. This method can be applied to either the case of laminating an adhesive layer on the uneven surface of the substrate and the case of laminating an adhesive layer on the smooth surface of the substrate. In addition, this method is particularly suitable for the case where an adhesive layer is laminated on the aforementioned uneven surface. The reason is that when this method is applied, a high effect of suppressing the generation of voids between the aforementioned uneven surface of the base material and the adhesive layer can be obtained.

On the other hand, when the adhesive layer is laminated on the substrate, as described above, the following method can also be applied instead of the method of applying the adhesive composition on the substrate. That is, the adhesive layer can also be laminated on the substrate by the following method: apply the adhesive composition on the release film and dry it if necessary, thereby forming an adhesive layer on the release film in advance to make the adhesive The exposed surface of the agent layer is attached to one surface of the substrate. In addition, this method is particularly suitable for the case where an adhesive layer is laminated on the aforementioned smooth surface. The reason is that when this method is applied, a high effect of suppressing the generation of voids between the smooth surface of the substrate and the adhesive layer can be obtained.

In the foregoing, the case where the adhesive layer is laminated on the substrate is cited as an example, but the above method can also be applied to, for example, the case where the aforementioned other layers are laminated on the substrate.

On the other hand, for example, when the protective film forming film is laminated on the adhesive layer already laminated on the substrate, the protective film forming composition can be coated on the adhesive layer to directly form the protective film forming film. The layer other than the film for forming a protective film can also use the composition for forming the layer, and the layer is laminated on the adhesive layer by the same method. In this way, a new layer (hereinafter, abbreviated as the "second layer") is formed on any layer (hereinafter, abbreviated as the "first layer") that has been laminated on the substrate to form a continuous two-layer laminated structure (in other words , In the case of a layered structure of the first layer and the second layer), it can be applied to the method of coating the composition for forming the second layer on the first layer and drying it if necessary. However, it is preferable to form a continuous two-layer laminated structure by using a composition for forming the second layer, and forming the second layer on the release film in advance so that The exposed surface on the opposite side to the side in contact with the release film is bonded to the exposed surface of the first layer. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. The peeling film can be removed as needed after forming the laminated structure. Here, the case where the protective film forming film is laminated on the adhesive layer is taken as an example, but for example, the case where the aforementioned other layers are laminated on the adhesive layer, etc., the target laminated structure can be arbitrarily selected.

In this way, all layers other than the base material constituting the protective film forming composite sheet can be laminated by the method of pre-formed on the release film and then bonded to the surface of the target layer. Therefore, as long as you need to appropriately select and adopt such a step What is necessary is just to manufacture a composite sheet for protective film formation by layer.

In addition, the composite sheet for forming a protective film is usually stored in a state where a release film is attached to the surface of the outermost layer (for example, the film for forming a protective film) on the opposite side to the antifouling sheet of the composite sheet for forming a protective film. Therefore, a composite sheet for forming a protective film with a release film is obtained by coating the release film (preferably the release treatment surface of the release film) with a composition for forming a protective film, etc. to form the outermost layer If necessary, dry the composition of the layer to form the outermost layer on the release film in advance. Use any of the above methods on the exposed surface of the layer opposite to the side contacting the release film Laminate the remaining layers without removing the release film and keep the attached state unchanged.

◇Method of manufacturing semiconductor chip with protective film The aforementioned composite sheet for forming a protective film can be used to manufacture a semiconductor wafer with a protective film. That is, the method for manufacturing a semiconductor chip with a protective film according to an embodiment of the present invention is to manufacture a semiconductor chip with a protective film provided with a semiconductor chip and a protective film provided on the inner surface of the semiconductor chip; the protective film is made of The protective film formation film in the aforementioned protective film formation composite sheet is formed; when the protective film formation film is curable, the cured product of the protective film formation film is a protective film, which is used for the formation of the protective film When the film is non-curable, the film for forming the protective film after being attached to the inner surface of the semiconductor wafer before being divided into the semiconductor wafer is a protective film; the manufacturing method of the semiconductor chip with protective film has: 1 The attaching step is to stretch the composite sheet for forming a protective film in a direction parallel to the attaching surface of the semiconductor wafer in the composite sheet for forming a protective film, while forming the protective film The protective film forming film in the composite sheet is attached to the entire inner surface of the semiconductor wafer whose size is smaller than the protective film forming film, so that the protective film forming is provided on the inner surface of the semiconductor wafer The first laminated body of the composite sheet; the first cutting step is to cut the composite sheet for forming the protective film in the first laminated body along the outer periphery of the semiconductor wafer, thereby making the semiconductor wafer The second laminated body of the composite sheet for forming the protective film after being cut is provided on the inner surface; the operation step is to operate the second laminated body; the second attaching step is after the operation step and after the operation In the antifouling sheet in the second layered body, the adhesive sheet is attached to the side opposite to the side of the protective film forming film or the protective film; the dividing step is after the second attaching step, and the semiconductor is divided The second cutting step is to cut the protective film forming film or protective film after the second attaching step; and the picking step is to provide the cut protective film The semiconductor wafer of the formation film or the protective film is pulled away from the laminated sheet including the antifouling sheet and the adhesive sheet and picked up; in the first attaching step, the composite sheet for the protective film formation is made to be opposite to the protective film The maximum width of the composite sheet for film formation in a direction parallel to the attachment surface of the semiconductor wafer is relative to the semiconductor wafer with respect to the composite sheet for protective film formation in the semiconductor wafer The maximum value of the width of the attachment surface in the parallel direction becomes 101.1% to 129.3%; when the film for forming the protective film is curable, there is a curing step, which is followed by the above-mentioned operation step to make the protective film The film for film formation is cured, thereby forming a protective film.

According to the above-mentioned method for manufacturing a semiconductor wafer with a protective film, it is possible to prevent unexpected foreign matter from adhering to the protective film forming film, especially the protective film, during the period from the beginning of the operation step to the beginning of the second attaching step. In the formation film, the surface on the opposite side to the attaching surface of the semiconductor wafer. Hereinafter, each step will be described in detail while referring to the drawings.

[Manufacturing method (1)] First, the manufacturing method (in this specification, sometimes referred to as "manufacturing method (1)") when there is the aforementioned curing step is described below. In the manufacturing method (1), since the film for forming a protective film is curable, the cured product of the film for forming a protective film is a protective film. FIGS. 5A to 5D and FIGS. 6A to 6C are cross-sectional views for schematically illustrating an example of the aforementioned manufacturing method (1). Here, the manufacturing method in the case of using the composite sheet 101 for forming a protective film shown in FIG. 1 is demonstrated.

[First attaching step] In the first attaching step of the manufacturing method (1), as shown in FIG. 5A, the protective film forming film 13 in the protective film forming composite sheet 101 is attached to a size smaller than that of the protective film forming film 13 The entire surface of the inner surface 9b of the semiconductor wafer 9. At this time, the composite sheet 101 for forming a protective film is formed on the bonding surface (that is, the first surface 13a of the film 13 for forming a protective film) to the semiconductor wafer in the composite sheet 101 for forming a protective film. While being stretched in a parallel direction, the composite sheet 101 for forming a protective film is attached to the inner surface 9 b of the semiconductor wafer 9. Thereby, the first laminated body 901 of the composite sheet 101 for forming a protective film is provided on the inner surface 9 b of the semiconductor wafer 9. In FIGS. 5A to 5D, reference numeral 9a denotes the surface of the semiconductor wafer 9 on the opposite side to the aforementioned inner surface 9b, that is, the circuit formation surface (the surface on which the circuit is formed).

In the above-mentioned first attaching step, as described above, when the protective film forming film 13 is attached to the entire inner surface 9b of the semiconductor wafer 9 while the protective film forming composite sheet 101 is stretched, antifouling The sheet 10 will not be cut, or wrinkles will not be generated, showing good sticking adaptability. The reason is that the aforementioned test piece of the antifouling sheet 10 has the above-mentioned 15% elongation.

In the aforementioned first attaching step, as the composite sheet 101 for forming a protective film, the size of the protective film forming film 13 is larger than the size of the semiconductor wafer 9 (in other words, the area of the first surface 13a of the protective film forming film 13 is larger than The area of the inner surface 9b of the semiconductor wafer 9) is a composite sheet for forming a protective film. Thereby, the protective film forming film 13 can be attached to the entire surface of the inner surface 9b of the semiconductor wafer 9.

The direction in which the composite sheet 101 for forming a protective film is stretched may be, for example, all directions parallel to the attachment surface.

When attaching the protective film forming composite sheet 101 to the semiconductor wafer 9, for example, it is preferable to use a method in which the area near the outer periphery of the semiconductor wafer 9 in the protective film forming composite sheet 101 is extended by about 10%. The composite sheet 101 for forming a protective film is stretched. Here, the aforementioned area of the composite sheet 101 for forming a protective film includes a portion to be cut in the first cutting step described later.

When the composite sheet 101 for forming a protective film is stretched, the tension applied to the sheet 101 is not particularly limited.

In the aforementioned first attaching step, the protective film forming film 13 may be heated to soften it and attached to the semiconductor wafer 9. In addition, the bumps and the like on the circuit formation surface 9a of the semiconductor wafer 9 are omitted here.

Furthermore, in the aforementioned first attaching step, the protective film forming composite sheet 101 is made to face the attaching surface 101a of the semiconductor wafer 9 in the protective film forming composite sheet 101 (that is, the protective film forming film The first surface 13a of 13 is _{the maximum value of the width W 101} in the parallel direction, and is relative to the attaching surface of the semiconductor wafer 9 to the protective film forming composite sheet 101 (that is, _{The maximum value of the width W 9} in the direction in which the inner surface 9b is parallel is 101.1% to 129.3%. Thereby, the subsequent first cutting step can be easily performed. More specifically, by setting _{the maximum value of the width W 101} to 101.1% or more of the maximum value of the width W ₉ , it is easy to recover the cut portion of the protective film forming composite sheet 101 in the first cutting step. By making the maximum value of the width W ₁₀₁ relative to the maximum value of the width W ₉ 129.3% or less, the operability of the first laminate 901 is improved, and further, the cost can be reduced by reducing the waste amount of the composite sheet 101 for forming a protective film .

In addition, FIG. 5A shows the cross section of the protective film forming composite sheet 101 and the semiconductor wafer 9 at the position where the _{aforementioned width W 101} and the aforementioned width W _{9 both become the largest, in FIGS. 5B to 5D and FIGS. 6A to 6C} The cross section of the object at the same part is also displayed.

As a preferable semiconductor wafer 9, as described above, a semiconductor wafer having a diameter of 150 mm, 200 mm, 300 mm, and 450 mm can be cited. The thickness of the semiconductor wafer 9 is not particularly limited. In terms of the strength of the semiconductor wafer 9 and easier division into semiconductor wafers described later, it is preferably 30 μm to 500 μm, and more preferably 50 μm to 400 μm.

In order to make the thickness of the semiconductor wafer 9 a target value, the inner surface of the semiconductor wafer 9 may be ground. That is, the inner surface 9b of the semiconductor wafer 9 may be a grinding surface.

Before the first attaching step, when the first inner surface of the semiconductor wafer 9 is ground, a back polishing tape for protecting the circuit forming surface 9a is usually attached to the circuit forming surface 9a of the semiconductor wafer 9. In the first attaching step, the circuit formation surface 9a of the semiconductor wafer 9 as the attaching target of the protective film forming composite sheet 101 may or may not attach the backside polishing tape. That is, the first layered body 901 may include the semiconductor wafer 9, the protective film forming composite sheet 101 provided on the inner surface 9b of the semiconductor wafer 9, and the back polishing of the circuit forming surface 9a provided on the semiconductor wafer 9 Tape (not shown).

[First Cutting Step] In the aforementioned first cutting step of the manufacturing method (1), the protective film forming composite sheet 101 in the first laminate 901 is cut along the outer periphery of the semiconductor wafer 9. As a result, as shown in FIG. 5B, the second laminated body 901 ′ of the composite sheet 101 for forming a protective film after being cut is provided on the inner surface 9 b of the semiconductor wafer 9. The maximum value _{of the width W 101} ′ of the composite sheet 101 for forming a protective film after cutting is equal to or less than the maximum value of _{W 101} , and equal to or more than the maximum value of _{W 9.}

In the aforementioned first cutting step, for example, a composite sheet for forming a protective film whose overall planar shape is rectangular or tape-like as shown in FIG. 2 can be used. In this case, the first attaching step is performed by continuously attaching a plurality of semiconductor wafers to one composite sheet for forming a protective film from one end side in the longitudinal direction of the composite sheet for forming a protective film toward the other end side. Then, by continuously cutting the composite sheet for forming a protective film in the above-described manner and performing the first cutting step, a plurality of second layered bodies 901' can be continuously produced. In addition, the first attaching step is performed by attaching one semiconductor wafer to one composite sheet for forming a protective film, and then the first cutting is performed by cutting the composite sheet for forming a protective film as described above. Step, the first attaching step and the first cutting step are repeated multiple times from one end side in the longitudinal direction of the composite sheet for forming a protective film toward the other end side, whereby a plurality of second laminated bodies 901' can be continuously produced .

In the aforementioned first cutting step, the composite sheet 101 for forming a protective film in the first laminate 901 is easily cut, the generation of burrs on the cut surface is suppressed, and good cutting suitability is exhibited. The reason is that the composite sheet 101 for forming a protective film in the first layered body 901 is provided on the inner surface 9b of the semiconductor wafer 9 while maintaining the state stretched in the above-mentioned manner. Furthermore, the aforementioned test piece of the antifouling sheet 10 has the above-mentioned The tensile strength at 10% elongation.

In this way, the protective film forming composite sheet 101 has good adhesion adaptability in the first attaching step, and good cutting adaptability in the first cutting step, so that it can be cut according to the size of the semiconductor wafer 9 The size of the composite sheet 101 for forming a protective film was adjusted well.

In the aforementioned first cutting step, _{the maximum value of the width W 101} of the protective film forming composite sheet 101 relative to the maximum value of the width W ₉ of the semiconductor wafer 9 is 101.1% to 129.3%, whereby the first laminate can be 901 is installed inside a normal cutting device without any problems.

[Steps] The type of operation of the second laminate 901' in the operation steps of the manufacturing method (1) is not particularly limited, and can be arbitrarily selected according to the purpose.

The antifouling sheet 10 is attached to the surface 13b on the opposite side to the first surface 13a of the protective film forming film 13 in the second layered body 901' (in this specification, it may be referred to as the "second surface"). Therefore, in the operation step, regardless of the type of operation of the second laminate 901', it is possible to prevent unintended foreign matter from adhering to the protective film forming film 13 in the second laminate 901', especially adhering to the protective film. The second surface 13b of the film 13 is used. In this way, the protective film forming composite sheet 101 forms a protective film on the inner surface 9b of the semiconductor wafer 9 by the protective film forming film 13. Not only that, when the second layered body 901' is operated before the semiconductor wafer 9 is divided, The antifouling sheet 10 suppresses unintended foreign matter from adhering to the protective film forming film 13.

Preferably, the foregoing operation steps are, for example, a printing step of printing (laser printing) by irradiating the film 13 for forming a protective film in the second laminate 901' with laser light L as shown in FIG. 5C. Laser printing can be performed by irradiating the film 13 for forming a protective film in the second layered body 901' with laser light L from the outside of the second layered body 901' on the side of the antifouling sheet 10 through the antifouling sheet 10. At this time, printing (not shown) is performed on the second surface 13b of the protective film forming film 13. Here, a new symbol 902 is assigned to the second layered body 901' after laser printing.

When the foregoing operation step is the foregoing printing step, _{the maximum value of the width W 101} ′ of the composite sheet 101 for forming a protective film after being cut is equal to or less than the maximum value of the foregoing W ₁₀₁ , and the second laminate can be 901' is installed inside a normal laser printing device without any problems.

As the operation of the second laminated body 901' other than the laser printing in the above-mentioned operation steps, there may be mentioned transportation of moving the second laminated body 901' to a target location. That is, as the aforementioned operation steps other than the printing step, a conveying step or the like can be cited.

In the printing step of the manufacturing method (1), the transparency of the anti-fouling sheet 10 is higher, for example, when it is 100 or more, the printing can be more clearly printed. In addition, after the printing step, the transparency of the antifouling sheet 10 becomes higher. For example, when it is 100 or more, the laser printing formed on the protective film forming film 13 or the protective film passes through the antifouling sheet 10 The visibility of laser printing has become higher.

The operation (in other words, the operation procedure) of the second layered body 901' may be only one type or two or more types, which can be arbitrarily set according to the purpose. In addition, the number of operations (in other words, the number of operation steps) may be only 1, or may be 2 or more, and can be arbitrarily set according to the purpose. For example, in the manufacturing method (1), as the aforementioned operation steps, the printing step and the conveying step may be performed together. In this case, the conveying step, the printing step, and the conveying step may be sequentially performed. However, this is an example when the number of operation steps is 2 or more.

[Hardening step] The manufacturing method (1) has a hardening step of hardening the film for forming the protective film after the above-mentioned operation step. In the manufacturing method (1), regardless of the presence or absence of cutting, the cured product obtained by curing the protective film formation film 13 attached to the semiconductor wafer 9 is used as the protective film.

Here, as shown in FIG. 5D, after the operation step (ie, the printing step) and before the second attaching step described later, the protective film forming film 13 in the second laminate 902 that has been laser-printed is displayed. It hardens to become the protective film 13'. However, in this embodiment, the timing of the hardening step is not limited to this as long as it is after the operation step. Here, the second laminate 902 after the protective film formation film 13 is cured is given a new symbol 902', and the protective film formation composite sheet 101 after the protective film formation film 13 is cured is given a new symbol 101'. The symbol 13a' indicates the first surface of the protective film 13', and the symbol 13b' indicates the second surface of the protective film 13'.

In the aforementioned curing step, when the protective film formation film 13 is thermosetting, the protective film formation film 13 is cured by heating to form the protective film 13'. When the protective film formation film 13 is energy ray curable, the protective film formation film 13 is cured by irradiating the protective film formation film 13 with energy rays through the antifouling sheet 10 to form the protective film 13 ′.

In the aforementioned curing step, the curing conditions of the protective film forming film 13, that is, the heating temperature and heating time during thermal curing, and the illuminance and light intensity of the energy beam during energy beam curing are as described above.

[Second attachment step] In the second attaching step of the manufacturing method (1), as shown in FIG. 6A, after the operation step, the laminated body after the operation (here, the laser printing is completed and the protective film formation film 13 is cured) The surface of the antifouling sheet 10 in the 2 layered body 902') opposite to the protective film 13' side (in this specification, sometimes referred to as the "second surface") 10b is attached to the adhesive sheet 8. Here, the second surface 10b of the antifouling sheet 10 has the same meaning as the second surface 11b of the base material 11.

The adhesive sheet 8 should just be able to fix the composite sheet 101 for protective film formation, and may be a well-known adhesive sheet. The adhesive sheet may also be a cutting sheet used in various cutting, for example.

As the adhesive sheet 8 more specifically, for example, an adhesive sheet composed only of a base material; an adhesive sheet provided with a base material and an adhesive layer formed on one surface of the aforementioned base material; The intermediate layer on one side of the substrate, and the adhesive sheet of the adhesive layer formed on the surface of the intermediate layer opposite to the substrate side. When using the adhesive sheet 8 with a layer other than the base material (for example, the aforementioned adhesive layer, the aforementioned intermediate layer, etc.), the base material is the outermost layer on the opposite side to the antifouling sheet 10 side (in other words, the base material is not As a method of attaching the antifouling sheet 10), an adhesive sheet 8 is arranged on the antifouling sheet 10.

In addition, in this specification, when it is necessary to consider both the antifouling sheet and the adhesive sheet, the base material in the antifouling sheet is referred to as the third substrate, and the adhesive layer in the antifouling sheet is referred to as the third adhesive. Floor. In addition, the base material in the adhesive sheet is referred to as the second base material, and the adhesive layer in the adhesive sheet is referred to as the second adhesive layer.

In the aforementioned second attaching step, the adhesive sheet 8 can also be softened by heating it, and then attached to the antifouling sheet 10.

[Division step, 2nd cutting step] In the manufacturing method (1), after the second attaching step, a dividing step of producing a semiconductor wafer 9'by dividing the semiconductor wafer 9 and a second cutting step of cutting the protective film 13' are performed. The order of performing the aforementioned dividing step and the second cutting step can be arbitrarily selected according to the purpose, the second cutting step can be performed after the dividing step, the dividing step and the second cutting step can also be performed at the same time, and the second cutting step can also be performed After the step, the segmentation step is performed. In the manufacturing method (1), when the division of the semiconductor wafer and the cutting of the protective film formation film or the protective film are continuously performed by the same operation without interruption in any order, it is regarded as simultaneous division Step and the second cutting step.

By performing the aforementioned dividing step and the second cutting step, as shown in FIG. 6B, a semiconductor chip 9'and a cut protective film 130' provided on the inner surface 9b' of the semiconductor wafer 9'are obtained. A semiconductor chip 91 with a protective film. In this step, a group of semiconductor wafers with a protective film 903 in a state where all of the plurality of semiconductor wafers with a protective film 91 are arranged on one antifouling sheet 10 is obtained. In FIGS. 6B to 6C, the symbol 9a' denotes the surface of the semiconductor wafer 9'on the opposite side to the aforementioned inner surface 9b', that is, the circuit forming surface (the surface on which the circuit is formed). In addition, the symbol 130a' indicates the surface of the cut protective film 130' that is on the opposite side to the adhesive layer 12 side (in this specification, it may be referred to as the "first surface"), and the symbol 130b' indicates the protection after cutting The film 130' is a surface on the opposite side to the first surface 130a' (in this specification, it may be referred to as a "second surface").

Both the aforementioned dividing step and the second cutting step can be performed by a known method according to the order in which these steps are performed.

In the case where the second cutting step is performed after the above-mentioned dividing step, the dividing (in other words, singulation) of the semiconductor wafer 9 can be performed by, for example, Stealth Dicing (registered trademark) or laser cutting. . Stealth cutting (registered trademark) is the following method. That is, first, a predetermined division portion is set inside the semiconductor wafer 9, and laser light is irradiated with the portion as the focal point and focused toward the focal point, thereby forming a modified layer inside the semiconductor wafer 9 (illustration omitted) Show). The modified layer of the semiconductor wafer 9 is different from other parts of the semiconductor wafer 9 in that it is deteriorated by irradiating laser light, and its strength becomes weaker. Therefore, by applying force to the semiconductor wafer 9, the modified layer inside the semiconductor wafer 9 produces turtles extending in the direction of both sides of the semiconductor wafer 9 (that is, the circuit forming surface 9a and the inner surface 9b). The crack becomes the starting point of the division (cutting) of the semiconductor wafer 9. Then, a force is applied to the semiconductor wafer 9, and the semiconductor wafer 9 is divided at the portion of the aforementioned modified layer to produce a semiconductor wafer 9'.

In the case where the second cutting step is performed after the aforementioned dividing step, the protective film 13' can be cut, for example, by aligning the protective film 13' along the surface of the protective film 13' to which the semiconductor chip 9 is attached. (That is, the first surface 13a') is stretched in a parallel direction (that is, so-called expansion). The expanded protective film 13 ′ is cut along the outer periphery of the semiconductor wafer 9. Such cutting by extension is preferably performed at a low temperature such as -20°C to 5°C.

When the aforementioned dividing step and the second cutting step are performed at the same time, various types of cutting can be performed, such as cutting with a blade using a blade, laser cutting with laser irradiation, or water cutting with water spray containing abrasives. At the same time, the division of the semiconductor wafer 9 and the cutting of the protective film 13' are performed. In addition, the semiconductor wafer 9 with a modified layer formed by stealth dicing (registered trademark) without being divided and the protective film 13' are expanded by the same method as above, whereby the semiconductor wafer 9 can also be simultaneously expanded Dividing and cutting off the protective film 13'.

In the case of performing the aforementioned dividing step after the aforementioned second cutting step, the protective film 13' can be cut without dividing the semiconductor wafer 9 without dividing the semiconductor wafer 9 by the same method for each cutting as described above, and then, The semiconductor wafer 9 is divided by breaking.

[Pickup Step] In the pick-up step of the manufacturing method (1), as shown in FIG. 6C, the semiconductor chip 9'with the cut protective film 130', that is, the protective film-attached semiconductor chip 91 is self-contained with the antifouling sheet 10 and the adhesive sheet The 8 laminated pieces 810 are pulled apart and picked up. Here, arrow I indicates the pick-up direction. The semiconductor wafer 91 with a protective film can be picked up by a well-known method. For example, as the pulling-off mechanism 7 for pulling the protective film-attached semiconductor wafer 91 from the laminated sheet 810, a vacuum collet or the like can be cited. In addition, in FIG. 6C, only the pull-off mechanism 7 is shown in cross section, which is the same in the same subsequent drawings. Through the above steps, the target semiconductor chip 91 with a protective film is obtained.

In the picking step, the antifouling sheet 10 can also be expanded in a direction parallel to the surface of the antifouling sheet 10 on the side of the protective film (ie, the first surface 10a), while picking up the semiconductor wafer with the protective film 91.

[Timing of the hardening step] In the foregoing, the case where the hardening step is performed between the operation step (for example, the printing step) and the second attaching step has been described, but in the manufacturing method (1), the timing of the hardening step is not limited to this . For example, in the manufacturing method (1), the curing step may be between the second attaching step and the dividing step, between the second attaching step and the second cutting step, between the dividing step and the picking step, between the cutting step and the cutting step. It is performed at any timing between the picking steps and after the picking step.

For example, in the above-mentioned second cutting step, when cutting the protective film forming film, as the cutting method of the protective film forming film, the above-mentioned cutting method of the protective film 13' can be applied. For example, in the aforementioned picking step, when picking up a semiconductor wafer with a protective film forming film formed of a semiconductor wafer and a protective film forming film provided on the inner surface of the semiconductor wafer, it is treated as the protective film The pick-up method of the semiconductor wafer of the film for film formation can apply the pick-up method of the semiconductor wafer 91 with a protective film mentioned above.

[Other steps] The manufacturing method (1) may be in addition to the first attaching step, the first cutting step, the operation step, the curing step, the second attaching step, the dividing step, the second cutting step, and the picking step mentioned above. There are other steps. The types of the aforementioned other steps and the timing of performing the aforementioned other steps can be arbitrarily selected according to the purpose, and are not particularly limited.

For example, when a back surface polishing tape is attached to the circuit forming surface 9a of the semiconductor wafer 9 used in the first attaching step, the manufacturing method (1) may include removing the back surface polishing tape from the circuit forming surface 9a. Remove the back grinding tape removal step. The timing of performing the back polishing tape removal step may be appropriately selected in consideration of all the conditions of the aforementioned manufacturing method, such as the method of the aforementioned dividing step and the second cutting step. In the case of performing the back polishing tape removal step, the timing for performing the aforementioned hardening step may be selected from the group consisting of, for example, the back polishing tape removal step, the second attaching step, the dividing step, the second cutting step, and the picking step. Between 2 steps in the group.

For example, the manufacturing method (1) may have a method of washing the protective film-attached semiconductor wafer 91 or the protective film-attached semiconductor wafer group 903 with water between the aforementioned dividing step or the second cutting step and the aforementioned pickup step. Washing steps. In the aforementioned cleaning step, the cutting chips generated by the division of the semiconductor wafer 9 in the aforementioned dividing step or the cutting chips generated by the cutting of the protective film 13' in the aforementioned cutting step are washed away.

[Manufacturing method (2)] In the foregoing, the method of manufacturing a semiconductor wafer with a protective film in the case of having the aforementioned curing step has been described, but the manufacturing method of this embodiment may not have the aforementioned curing step. Next, the manufacturing method (in this specification, it may be referred to as "manufacturing method (2)") in the case of not having the aforementioned curing step will be described below. In the manufacturing method (2), since the film for forming a protective film is non-curable, the film for forming a protective film after being attached to the inner surface of the semiconductor wafer is a protective film. FIGS. 7A to 7C and FIGS. 8A to 8C are cross-sectional views for schematically explaining an example of the aforementioned manufacturing method (2).

[First attaching step] In the first attaching step of the manufacturing method (2), as shown in FIG. 7A, the protective film forming film 23 in the protective film forming composite sheet 103 is attached to a size smaller than that of the protective film forming film 23. The entire surface of the inner surface 9b of the semiconductor wafer 9. At this time, the composite sheet for forming a protective film 103 is stretched in a direction parallel to the attaching surface 103a of the semiconductor wafer in the composite sheet for forming a protective film 103, while the composite sheet for forming a protective film is stretched 103 is attached to the inner surface 9b of the semiconductor wafer 9. Thereby, the 1st laminated body 904 which provided the composite sheet|seat 103 for protective film formation on the inner surface 9b of the semiconductor wafer 9 was produced. In FIGS. 7A to 7C, the symbol 23a indicates the surface of the protective film forming film 23 on the semiconductor wafer 9 side (in this specification, it may be referred to as the "first surface"), which is the same as the protective film forming composite sheet 103 This has the same meaning for the attachment surface 103a of the semiconductor wafer 9.

In the first attaching step, as described above, when the protective film forming film 23 is attached to the entire inner surface 9b of the semiconductor wafer 9 while the protective film forming composite sheet 103 is stretched, the antifouling sheet 10 will not be cut, and will not produce wrinkles, showing good adherence. The reason is that the aforementioned test piece of the antifouling sheet 10 has the above-mentioned 15% elongation.

In the aforementioned first attaching step, as the protective film forming composite sheet 103, the protective film forming film 23 is used. The size of the protective film forming film 23 is larger than the size of the semiconductor wafer 9 (in other words, the area of the first surface 23a of the protective film forming film 23 is A composite sheet for forming a protective film larger than the area of the inner surface 9b of the semiconductor wafer 9). Thereby, the protective film forming film 23 can be attached to the entire inner surface 9b of the semiconductor wafer 9.

In the manufacturing method (2), the protective film forming film 23 can be used as a protective film in its original state without curing, and the protective film after being attached to the inner surface 9b of the semiconductor wafer 9 in the first attaching step is formed The film 23 is regarded as a protective film 23. The composite sheet 103 for protective film formation is the same as the composite sheet 101 for protective film formation mentioned above except the point provided with the film 23 for protective film formation instead of the film 13 for protective film formation.

This step can be performed by the same method as in the case of the first attaching step in the manufacturing method (1), except that the composite sheet 103 for forming a protective film is used instead of the composite sheet 101 for forming the protective film. For example, in the first attaching step of the manufacturing method (2), the protective film forming composite sheet 103 is made to face the attaching surface 103a (that is, to the semiconductor wafer 9) of the protective film forming composite sheet 103 , The first surface 23a) of the protective film forming film 23 has _{the maximum value of the width W 103} in the parallel direction, relative to the semiconductor wafer 9 with respect to the protective film forming composite sheet 103 _{The maximum value of the width W 9} in the parallel direction of the attachment surface (ie, the inner surface) 9b becomes 101.1% to 129.3%. Thereby, the subsequent first cutting step can be easily performed. More specifically, by making _{the maximum value of the width W 103} relative to the maximum value of the width W ₉ 101.1% or more, it is easy to recover the cut portion of the protective film forming composite sheet 103 in the first cutting step . By making the maximum value of the width W ₁₀₃ relative to the maximum value of the width W ₉ 129.3% or less, the operability of the first laminate 904 is improved, and further, the cost can be reduced by reducing the waste amount of the composite sheet 103 for forming a protective film .

In addition, in FIG. 7A, similar to the case of FIG. 5A, the cross section of the protective film forming composite sheet 103 and the semiconductor wafer 9 _{where the aforementioned width W 103} and the aforementioned width W _{9 both become the largest is shown, and FIGS. 7B to} Fig. 7C and Figs. 8A to 8C also show the cross section of the object at the same position.

[First cutting step] In the aforementioned first cutting step of the manufacturing method (2), the protective film forming composite sheet 103 in the first laminate 904 is cut along the outer periphery of the semiconductor wafer 9. Thereby, as shown in FIG. 7B, the second laminated body 904' provided with the composite sheet 103 for forming a protective film after the cut is provided on the inner surface 9b of the semiconductor wafer 9 is produced.

This step can be performed by the same method as in the case of the first cutting step in the manufacturing method (1), except that the composite sheet 103 for forming a protective film is used instead of the composite sheet 101 for forming the protective film. For example, the maximum value _{of the width W 103} ′ of the composite sheet 103 for forming a protective film after being cut is equal to or less than the maximum value of _{W 103} , and equal to or more than the maximum value of _{W 9.}

For example, in the first cutting step of the manufacturing method (2), as in the case of the first cutting step of the manufacturing method (1), the overall planar shape as shown in FIG. 2 can be used as a rectangle or In this case, a strip-shaped composite sheet for forming a protective film can be used to continuously produce a plurality of second layered bodies 904' by the two methods described above.

In the aforementioned first cutting step, the composite sheet 103 for forming a protective film in the first laminate 904 is easily cut, the generation of burrs in the cut surface is suppressed, and good cutting suitability is exhibited. The reason is that the composite sheet 103 for forming a protective film in the first layered body 904 is provided on the inner surface 9b of the semiconductor wafer 9 while maintaining the state stretched in the above-mentioned manner. Furthermore, the aforementioned test piece of the antifouling sheet 10 has the above-mentioned The tensile strength at 10% elongation.

In this way, the protective film forming composite sheet 103 has good adhesion adaptability in the first attaching step, and good cutting adaptability in the first cutting step, so that it can be cut according to the size of the semiconductor wafer 9 The size of the composite sheet 103 for forming a protective film is adjusted well.

In the above-mentioned first cutting step, since _{the maximum value of the width W 103} of the protective film forming composite sheet 103 with respect to the maximum value of the width W ₉ of the semiconductor wafer 9 is 101.1% to 129.3%, the first laminate can be 904 is installed inside a normal cutting device without any problems.

[Steps] The type of operation of the second layered body 904' in the aforementioned operation steps of the manufacturing method (2) is the same as the type of operation of the second layered body 901' in the manufacturing method (1).

The antifouling sheet 10 is attached to the surface 23b on the opposite side to the first surface 23a of the protective film 23 in the second layered body 904' (in this specification, it may be referred to as the "second surface"). Therefore, in the operation step, regardless of the type of operation of the second layered body 904', it is possible to suppress the adhesion of unexpected foreign matter to the protective film 23 in the second layered body 904', especially the second layer of the protective film 23.面23b. In this way, the protective film forming composite sheet 103 forms a protective film with the protective film forming film 23 on the inner surface 9b of the semiconductor wafer 9. Not only that, the second laminated body 904' is formed before the division of the semiconductor wafer 9 During the operation, the antifouling sheet 10 prevents unintended foreign matter from adhering to the protective film forming film 23 (that is, the protective film 23).

Preferably, the foregoing operation steps are, for example, a printing step of printing (laser printing) by irradiating the protective film 23 in the second laminate 904' with laser light L as shown in FIG. 7C. Laser printing can be performed by irradiating the protective film 23 in the second layered body 904' with laser light L from the outside on the side of the antifouling sheet 10 of the second layered body 904' through the antifouling sheet 10. At this time, printing (not shown) is applied to the second surface 23 b of the protective film 23. In addition, here, a new symbol 905 is assigned to the second layered body 904' after laser printing.

In this step, the laser printing can be performed by the same method as the laser printing in the manufacturing method (1) except that the target of the laser light L is the protective film 23 instead of the protective film forming film 13. _{For example, since the maximum value of the width W 103} ′ of the composite sheet 103 for forming a protective film after being cut is equal to or less than the maximum value of the aforementioned W ₁₀₃ , the second layered body 904 ′ can be installed in a normal mine without problems. The inside of the printing device. In addition, the higher the transmission clarity of the antifouling sheet 10, for example, when it is 100 or more, the protective film 23 can be printed more clearly. Moreover, after the printing step, the transparency of the anti-fouling sheet 10 becomes higher. For example, when it is 100 or more, the visibility of the laser printing formed on the protective film 23 is changed by the laser printing of the anti-fouling sheet 10. Get higher.

[Second attachment step] In the foregoing second attaching step of the manufacturing method (2), as shown in FIG. 8A, after the foregoing operation steps, in the laminated body after the operation (here, the laser-printed second laminated body 905) The adhesive sheet 8 is attached to the surface 10b of the antifouling sheet 10 on the opposite side to the side of the protective film 23 (that is, the second surface). In this step, except that the object to be attached to the adhesive sheet 8 is the composite sheet 103 for forming a protective film instead of the composite sheet 101 for forming a protective film, the same as the case of the second attaching step in the manufacturing method (1) can be used. Method to proceed.

[Division step, 2nd cutting step] In the manufacturing method (2), after the second attaching step, the dividing step of producing the semiconductor wafer 9'by dividing the semiconductor wafer 9 and the second cutting step of cutting the protective film 23 are performed. The order of performing the aforementioned dividing step and the second cutting step is the same as in the case of the manufacturing method (1).

In the manufacturing method (2), by performing the aforementioned dividing step and the second cutting step, as shown in FIG. 8B, a protection after cutting including a semiconductor wafer 9'and an inner surface 9b' provided on the semiconductor wafer 9'is obtained A plurality of protective film-attached semiconductor wafers 92 constituted by a film 230. In this step, a group of semiconductor wafers with a protective film 906 in a state where all of these plurality of semiconductor wafers 92 with a protective film are arranged on one antifouling sheet 10 is obtained. In FIGS. 8B to 8C, the symbol 230a indicates the surface of the cut protective film 230 on the side opposite to the adhesive layer 12 side (in this specification, it may be referred to as the "first surface"), and the symbol 230b indicates the cut surface In the protective film 230, the surface on the opposite side to the first surface 230a (in this specification, it may be referred to as the "second surface").

The dividing step in the manufacturing method (2) can be performed by the same method as in the case of the dividing step in the manufacturing method (1). The second cutting step in the manufacturing method (2) can be the same as the second cutting step in the manufacturing method (1) except that the object of cutting is the protective film 23 instead of the protective film 13'. Method to proceed.

[Pickup Step] In the aforementioned pick-up step of the manufacturing method (2), as shown in FIG. 8C, the semiconductor chip 9'with the cut protective film 230, that is, the semiconductor chip 92 with the protective film, is self-contained with the antifouling sheet 10 and the adhesive sheet The 8 laminated pieces 810 are pulled apart and picked up. This step can be performed by the same method as in the case of the pickup step in the manufacturing method (1), except that the object to be picked up is the semiconductor wafer 92 with a protective film instead of the semiconductor wafer 91 with a protective film. Through the above steps, the target semiconductor chip 92 with a protective film is obtained.

[Other steps] The manufacturing method (2) may have other steps in addition to the first attaching step, the first cutting step, the operation step, the second attaching step, the dividing step, the second cutting step, and the picking step mentioned above. . However, the aforementioned other steps in the manufacturing method (2) do not include a curing step of curing the aforementioned protective film forming film after the aforementioned operation step. As the aforementioned other steps in the manufacturing method (2), the same steps as the aforementioned other steps in the manufacturing method (1) can be cited. The types of the aforementioned other steps and the timing of performing the aforementioned other steps can be arbitrarily selected according to the purpose, and are not particularly limited.

For example, when a back polishing tape is attached to the circuit forming surface 9a of the semiconductor wafer 9 used in the first attaching step, the manufacturing method (2) may include removing the back polishing tape from the circuit forming surface 9a. Remove the back grinding tape removal step. The timing of performing the back polishing tape removal step may be appropriately selected in consideration of all the conditions of the aforementioned manufacturing method, such as the method of the aforementioned dividing step and the second cutting step.

For example, the manufacturing method (2) may have a method of washing the protective film-attached semiconductor wafer 92 or the protective film-attached semiconductor wafer group 906 with water between the aforementioned dividing step or the second cutting step and the aforementioned pickup step. Washing steps. In the aforementioned cleaning step, the cutting chips generated by the division of the semiconductor wafer 9 in the aforementioned dividing step or the cutting chips generated by the cutting of the protective film 23 in the aforementioned cutting step are washed away.

In the foregoing, the method of manufacturing a semiconductor wafer with a protective film when the composite sheet 101 for forming a protective film shown in FIG. 1 is used has been mainly described. However, the method of manufacturing a semiconductor wafer with a protective film of this embodiment is not Not limited to this. For example, in the method of manufacturing a semiconductor wafer with a protective film of this embodiment, even if the protective film forming composite sheet 102 shown in FIG. 4 is used as a protective film forming composite sheet other than the protective film forming composite sheet 101 shown in FIG. It is also possible to manufacture semiconductor wafers with protective films in the same way. In this way, when the composite sheet for forming a protective film of another embodiment is used, based on the difference in structure between the composite sheet and the composite sheet for forming a protective film 101, it is appropriate to add, change, and delete steps in the above-mentioned manufacturing method. The semiconductor wafer can be manufactured by waiting.

The method for manufacturing a semiconductor chip with a protective film described in the foregoing may also have a method according to the semiconductor wafer after the step of attaching the composite sheet for forming a protective film to the semiconductor wafer (that is, the first attaching step) The step of cutting the composite sheet for forming a protective film to the size (that is, the first cutting step). Since the composite sheet for forming a protective film of this embodiment has the above-mentioned tensile properties (15% elongation, 10% elongation tensile strength), it can be well adjusted by cutting according to the size of the semiconductor wafer. The size of the composite sheet for forming a protective film. However, the composite sheet for forming a protective film of this embodiment can also be used in other methods.

For example, it is also possible to cut the composite sheet for forming a protective film according to the size of the target semiconductor wafer in advance, and attach the cut composite sheet for forming a protective film to the semiconductor wafer, and then use the same manufacturing method as described above. In the same way, a semiconductor wafer with a protective film is manufactured. For example, a method having the following steps corresponds to the method: using a composite sheet for forming a protective film whose overall planar shape is rectangular or strip-shaped as shown in FIG. 2, and attaching the composite sheet for forming a protective film to a semiconductor wafer Previously, it was cut in advance according to the size of the semiconductor wafer, and the obtained slice (for example, the slice whose overall planar shape was a circular shape) was used as the target protective film forming composite sheet and attached to the semiconductor wafer. If the cutting of the composite sheet for forming a protective film at this time is performed as a punching process, and the punching process is performed multiple times in the longitudinal direction of the composite sheet for forming a protective film before cutting, for example, as shown in FIG. 3 A composite sheet for forming a protective film of the constitution shown.

◇Method of manufacturing semiconductor device After the semiconductor chip with protective film is obtained by the above-mentioned manufacturing method, the semiconductor chip is flip-chip connected to the circuit forming surface of the substrate by a known method, and then a semiconductor package is made. The target semiconductor device (illustration omitted) can be manufactured. [Example]

Hereinafter, the present invention will be described in more detail with specific examples. However, the present invention is not limited at all to the examples shown below.

[Materials for the production of the protective film forming composition] The raw materials used to manufacture the protective film forming composition are shown below. [Polymer component (A)] (A)-1: Acrylic resin obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight 370,000, glass transition temperature 6°C). [Thermosetting component (B)] ・Epoxy resin (B1) (B1)-1: Bisphenol A epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184g/eq to 194g/eq) (B1)-2: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800g/eq to 900g/eq) (B1)-3: Dicyclopentadiene epoxy resin ("Epiclon HP-7200HH" manufactured by DIC, epoxy equivalent 255g/eq to 260g/eq) ・Thermal hardener (B2) (B2)-1: Dicyandiamide (thermally active latent epoxy resin hardener, "Adeka Hardener EH-3636AS" manufactured by ADEKA, active hydrogen content 21g/eq) [Hardening accelerator (C)] (C)-1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curezol 2PHZ" manufactured by Shikoku Chemical Industry Co., Ltd.) [Filling material (D)] (D)-1: Silica filler ("SC2050MA" manufactured by Admatechs, silica filler with epoxy compound surface modification, average particle size 500nm) [Coupling agent (E)] (E)-1: Silane coupling agent ("A-1110" manufactured by Nippon Unicar) [Colorant (I)] (I)-1: Organic black pigments ("6377 Black" manufactured by Dainichi Seiki Chemical Co., Ltd.)

[Example 1] [Manufacturing of composite sheet for protective film formation] [Manufacturing of composition for forming thermosetting protective film (III-1)] The polymer component (A)-1 (120 parts by mass), epoxy resin (B1)-1 (50 parts by mass), epoxy resin (B1)-2 (10 parts by mass), epoxy resin (B1)- 3 (30 parts by mass), thermosetting agent (B2)-1 (2 parts by mass), hardening accelerator (C)-1 (2 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E)-1 (2 parts by mass) and coloring agent (I)-1 (5 parts by mass) are mixed, and then diluted with methyl ethyl ketone to prepare the above-mentioned components with a total concentration of 55% by mass Composition for forming a thermosetting protective film (III-1).

[Manufacturing of protective film forming film] Use a peeling film made of polyethylene terephthalate on one side that has been peeled off by silicone treatment (the first peeling film, "SP-PET501031" made by Lindke, thickness 50μm), The peeling treatment surface of the peeling film is coated with the thermosetting protective film forming composition (III-1) obtained as described above, and heated and dried at 100°C for 2 minutes to produce a thermosetting tape with a thickness of 15 μm The protective film forming film. Next, a peeling film made of polyethylene terephthalate, one side of which was peeled off with silicone treatment (the second peeling film, "SP-PET381031" manufactured by Lindeco, thickness 38μm) The peeling treatment surface of the peeling film is attached to the exposed surface of the protective film forming film obtained above, thereby manufacturing the first peeling film, the protective film forming film, and the second peeling film in order of the thickness of these layers A band-shaped laminated film formed by layering in the direction.

[Manufacturing of Adhesive Composition (I-4)] Preparation of a non-energy-ray-curable adhesive composition (I-4), the adhesive composition (I-4) containing acrylic polymer (100 parts by mass) and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (18 parts by mass based on the amount of the aforementioned crosslinking agent), further containing methyl ethyl ketone as a solvent, and the total concentration of the aforementioned acrylic polymer and crosslinking agent It is 55% by mass. The aforementioned acrylic polymer is a copolymer having a weight average molecular weight of 800,000, which is obtained by copolymerizing 2-ethylhexyl acrylate (80 parts by mass) and 2-hydroxyethyl acrylate (20 parts by mass).

[Manufacturing of anti-fouling sheet] Use a peeling film made of polyethylene terephthalate, one side of which has been peeled off by silicone treatment ("SP-PET381031" made by Lindeco, thickness 38μm), on the above-mentioned peeling film The peeling treatment surface was coated with the adhesive composition (I-4) obtained above, and heated and dried at 100° C. for 2 minutes, thereby forming a non-energy-ray-curable adhesive layer with a thickness of 10 μm and a belt shape. Separately, a tape-shaped polypropylene substrate (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm) with a surface roughness Ra on one side smaller than that on the other side, an uneven surface on one side and a smooth surface on the other side, was prepared as a substrate. The above-obtained non-energy-ray-curable adhesive layer is laminated on the exposed surface of the aforementioned substrate to form a substrate, an adhesive layer, and a release film, which are laminated in the thickness direction of these layers in order. Strip-shaped antifouling sheet with peeling film.

[Manufacturing of composite sheet for protective film formation] The release film was removed from the antifouling sheet obtained above. In addition, the second release film was removed from the laminated film obtained above. And, the exposed surface of the adhesive layer newly generated in the antifouling sheet (in other words, the surface of the adhesive layer opposite to the substrate side) is compared with the first release film and protective film forming film obtained above. The exposed surface of the protective film formation film (in other words, the surface of the protective film formation film opposite to the first release film side) in the laminate. Thereby, the following composite sheet for forming a protective film with a first release film was obtained: base material (thickness 80μm), adhesive layer (thickness 10μm), protective film formation film (thickness 15μm), and first release film ( (Thickness: 50 μm) is formed by sequentially stacking these layers in the thickness direction, and the planar shape of all the layers is a belt shape with a width of 220 mm. Through the above steps, a composite sheet for forming a protective film having the configuration shown in FIG. 1 and having the target wafer size is produced. Table 1 shows each layer constituting the composite sheet for forming a protective film. When the column of layer is described as "-", it means that the composite sheet for forming a protective film does not have the layer.

[Evaluation of antifouling sheet, protective film forming film, and protective film forming composite sheet] [Determination of the clarity of antifouling sheet] The first release film was removed from the band-shaped antifouling sheet obtained above. Using an image clarity measuring device ("ICM-10P" manufactured by Suga Test Instruments), in accordance with JIS K 7374:2007, the width of the slit through which the irradiated light is transmitted is set to 0.125mm, 0.25mm, 0.5mm, 1mm And 5 types of 2mm, in each case, for the aforementioned antifouling sheet, the evaluation value of image clarity (image clarity) is obtained, and the total value of the evaluation value is used as the transmission clarity. The results are shown in Table 1.

[Evaluation of 15% extensibility of anti-fouling sheet] A piece of 15 mm in width was cut out from the strip-shaped antifouling sheet with the first release film obtained above, and the first release film was removed from the piece to prepare a test piece of 15 mm in width. In addition, in accordance with JIS K 7127: 1999 (ISO527-3: 1995) and JIS K 7161: 1994 (ISO 5271: 1993), the 15% extensibility of the aforementioned test piece (in other words, the antifouling sheet) was evaluated in the following order. That is, the following tensile test is performed: under the temperature condition of 18°C to 28°C, the initial chuck spacing is set to 100mm, and the test piece is set at 200mm in a direction parallel to the surface of the test piece. Stretching at a speed of /min. At this time, confirm whether the aforementioned test piece has elongation or breakage, and evaluate the 15% extensibility of the test piece (anti-fouling sheet) based on the following criteria. In the MD direction and the TD direction of the test piece, two different test pieces were used for the evaluation. The results are shown in Table 1. [Evaluation criteria] A: The test piece is not broken but is elongated by 15% or more in the tensile direction. B: The test piece broke before it was extended by 15% or more in the tensile direction.

[Tensile strength of anti-fouling sheet at 10% elongation] During the 15% elongation evaluation of the above-mentioned test piece (anti-fouling sheet), the tensile strength of the test piece (anti-fouling sheet) at 10% extension in the tensile direction was measured at the same time. In the MD direction and the TD direction of the test piece, two different test pieces were used for the measurement. The results are shown in Table 1.

[Evaluation of the visibility of laser printing of protective film formation film] Using a laminator for back polishing tape ("RAD3510" manufactured by Lindeco), the first release film was removed from the composite sheet for forming a protective film with a first release film obtained above. In addition, on the exposed surface of the protective film formation film in the protective film formation composite sheet, the entire inner surface of the semiconductor wafer having a diameter of 200 mm and a thickness of 350 μm was attached. At this time, under the conditions of an attaching pressure of 0.3 MPa and an attaching speed of 30 mm/s, the temperature of the worktable for attaching was set to 50° C., and the semiconductor wafer was attached to the composite sheet for forming a protective film. In addition, the composite sheet for forming a protective film is attached while being stretched in a direction parallel to the attaching surface to the semiconductor wafer in the composite sheet for forming a protective film.

Then, in the laminator described above, the protective film forming composite sheet is cut along the outer periphery of the semiconductor wafer to obtain a protective film formed with a semiconductor wafer and a cut located on the inner surface of the semiconductor wafer. The aforementioned second laminate of the composite sheet. At this time, the cutting speed of the composite sheet for forming a protective film was 200 mm/sec. In addition, the center of the protective film forming film after the cut was aligned with the center of the semiconductor wafer, and the layers were concentric in the second laminate. The composite sheet-based substrate (thickness 80μm), the adhesive layer (thickness 10μm) and the protective film formation film (thickness 15μm) in the second laminate obtained here are in the thickness direction of these layers in this order It is constructed by layering, and the planar shape of all these layers becomes a circular structure with a diameter of 200 mm.

From one end of the protective film forming composite sheet to the other end, the following steps were repeated in the aforementioned laminator 20 times in total to produce 20 second laminates: in the above-mentioned protective film forming composite sheet The exposed surface of the protective film formation film is attached to the entire inner surface of the semiconductor wafer, and the protective film formation composite sheet is cut along the outer periphery of the semiconductor wafer.

Then, one of the 20 second laminates obtained as described above was installed inside a laser printing device ("CSM3000" manufactured by EO Technics). This laser printing device corresponds to the operation of the printing object of the wafer size, but does not correspond to the operation of the printing object of the ring frame size. In addition, the protective film forming film in the second laminate is irradiated with laser light via the antifouling sheet (that is, the laminate of the base material and the adhesive layer), thereby irradiating the protective film forming film on the antifouling sheet side Laser printing is performed on the surface (that is, the second surface). At this time, the size of the printed characters is 0.3mm×0.2mm. In addition, the characters were visually observed through the antifouling sheet, and the laser printing visibility of the protective film formation film was evaluated based on the following criteria. The results are shown in Table 1. [Evaluation criteria] A: The text can be clearly recognized. B: The text is slightly blurred but visible. C: The text cannot be read.

[Evaluation of antifouling property of protective film formation film] After the above-mentioned evaluation of the visibility of the laser printing of the protective film forming film, the antifouling sheet was peeled off from the protective film forming film in the second laminate after the laser printing. In addition, the exposed surface of the protective film formation film was directly observed visually, and the antifouling properties of the protective film formation film were evaluated based on the following criteria. The results are shown in Table 1. [Evaluation criteria] A: No foreign matter adhered. B: Foreign matter adhered.

[Evaluation of the cutting suitability of the composite sheet for forming a protective film] Among the 20 second laminates obtained during the evaluation of the visibility of the laser printing of the protective film formation film described above, the cut surface of the protective film formation composite sheet was visually observed for each one to confirm the foregoing Whether there are burrs on the cut surface, the cutting suitability of the composite sheet for forming a protective film was evaluated based on the following criteria. The results are shown in Table 1. In Table 1, the number of sheets of the laminate with burrs on the cut surface is also expressed as "the number of sheets with burrs". [Evaluation criteria] A: The number of laminates with burrs is zero. B: The number of laminates with burrs is 1 to 4. C: The number of laminates with burrs is 5 or more.

[Evaluation of the abrasion inhibition of the blade of the cutter when cutting the composite sheet for forming a protective film] In the evaluation of the visibility of laser printing of the protective film forming film described above, the composite sheet for forming the protective film was cut to obtain 20 second laminates, and then the optical microscope manufactured by Keyence Corporation was used to observe the composite sheet. The blade of the cutter in the device used for cutting. In addition, the abrasion-suppressive properties of the blade of the cutter at the time of cutting the composite sheet for forming a protective film were evaluated based on the following criteria. The results are shown in Table 1. A: The blade of the cutter is not worn. B: The blade of the cutter is slightly worn, but it can be used directly. C: The blade of the cutter is more worn than in the case of B, but it can be used directly. D: The blade of the cutter is significantly worn and cannot be used directly.

[Manufacture of a composite sheet for forming a protective film, and evaluation of an antifouling sheet, a film for forming a protective film, and a composite sheet for forming a protective film] [Example 2] In the production of the adhesive composition (I-4), the content of the trifunctional xylylene diisocyanate-based crosslinking agent is set to 8 parts by mass instead of 18 parts by mass based on the amount of the aforementioned crosslinking agent. Otherwise, a composite sheet for forming a protective film was produced by the same method as in Example 1, and the antifouling sheet, the film for forming a protective film, and the composite sheet for forming a protective film were evaluated. The results are shown in Table 1.

[Example 3] [Manufacturing of composite sheet for protective film formation] [Manufacturing of Adhesive Resin (I-2a)] The weight is prepared by copolymerizing 2-ethylhexyl acrylate (hereinafter referred to as "2EHA") (80 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (20 parts by mass) An acrylic polymer with an average molecular weight of 800,000. Add 2-methacryloxyethyl isocyanate (22 parts by mass, about 80 mol% relative to HEA) to the acrylic polymer, and perform an addition reaction at 50°C for 48 hours in an air stream. Thus, the adhesive resin (I-2a) is obtained.

[Manufacturing of Adhesive Composition (I-2)] An energy-ray curable adhesive composition (I-2) is prepared, the adhesive composition (I-2) contains the adhesive resin (I-2a) (100 parts by mass) obtained above, and a trifunctional xylylene -Based diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (5 parts by mass based on the amount of the crosslinking agent), further containing methyl ethyl ketone as a solvent, and the aforementioned adhesive resin The total concentration of (I-2a) and the crosslinking agent is 55% by mass.

[Manufacturing of anti-fouling sheet] Using the same release film as the release film used in Example 1 ("SP-PET381031" manufactured by Lindeco, thickness 38μm), the adhesive composition obtained above was applied to the release treatment surface of the release film ( I-2) Heat and dry at 100°C for 2 minutes to form a band-shaped energy-ray-curable adhesive layer with a thickness of 10 μm. Separately, a tape-shaped polypropylene substrate (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm) as the substrate used in Example 1 was prepared. The above-mentioned exposed surface of the energy-ray-curable adhesive layer is bonded to the uneven surface of the aforementioned substrate, thereby producing a substrate, an adhesive layer, and a release film that are laminated in the thickness direction of these layers in order to form an attachment. Strip-shaped anti-fouling sheet for peeling film.

[Manufacturing of composite sheet for protective film formation] Except for the use of the antifouling sheet obtained above, the same method as in the case of Example 1 was used to produce a belt-shaped composite sheet for forming a protective film and a second laminate.

[Evaluation of antifouling sheet, protective film forming film, and protective film forming composite sheet] The antifouling sheet, protective film forming film, and protective film forming composite sheet obtained above were evaluated in the same manner as in the case of Example 1. The results are shown in Table 1.

[Manufacture of a composite sheet for forming a protective film, and evaluation of an antifouling sheet, a film for forming a protective film, and a composite sheet for forming a protective film] [Example 4] In the production of the antifouling sheet, a tape-shaped polyethylene terephthalate substrate (manufactured by Toyobo Co., Ltd., thickness 100μm) with smooth surfaces on both sides is used instead of the tape-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy-ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture protective film formation Composite sheet, evaluation of antifouling sheet, protective film formation film, and protective film formation composite sheet. The results are shown in Table 1.

[Example 5] In the production of the antifouling sheet, a tape-shaped polypropylene substrate (manufactured by Gunze Corporation, thickness 80μm) with concave and convex surfaces on both sides is used instead of the aforementioned tape-shaped polypropylene substrate (manufactured by Mitsubishi Plastics Corporation, thickness 80μm) , Attach one of the uneven surfaces to the exposed surface of the non-energy-ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to produce a composite sheet for forming a protective film, and the antifouling was evaluated Sheet, protective film forming film, and protective film forming composite sheet. The results are shown in Table 1.

[Example 6] In the production of the antifouling sheet, a tape-shaped polypropylene substrate (manufactured by RIKEN TECHNOS, thickness 60μm) with an uneven surface on one side and a smooth surface on the other side is used instead of the tape-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), the uneven surface of the substrate is attached to the exposed surface of the non-energy-ray-curable adhesive layer, except for this point, the protective film is manufactured by the same method as in Example 1 The composite sheet for formation was evaluated for the antifouling sheet, the film for forming a protective film, and the composite sheet for forming the protective film. The results are shown in Table 1.

[Example 7] During the production of the antifouling sheet, the smooth surface of the base material was attached to the exposed surface of the non-energy ray-curable adhesive layer instead of the uneven surface. Except for this point, the same as in Example 1 was used. Methods: A composite sheet for forming a protective film was manufactured, and the antifouling sheet, a film for forming a protective film, and a composite sheet for forming a protective film were evaluated. The results are shown in Table 1.

[Example 8] In the production of the antifouling sheet, a tape-shaped polyethylene terephthalate substrate (manufactured by Toyobo Co., Ltd., thickness 38μm) with smooth surfaces on both sides is used instead of the tape-shaped polypropylene substrate (Mitsubishi Plastics Corporation) Manufacturing, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture a protective film forming composite Sheets were evaluated for antifouling sheets, protective film formation films, and protective film formation composite sheets. The results are shown in Table 1.

[Example 9] In the production of the antifouling sheet, a tape-shaped polyethylene terephthalate substrate (manufactured by Toyobo Co., Ltd., thickness 25μm) with smooth surfaces on both sides is used instead of the tape-shaped polypropylene substrate (Mitsubishi Plastics Corporation) Manufacturing, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture a protective film forming composite Sheets were evaluated for antifouling sheets, protective film formation films, and protective film formation composite sheets. The results are shown in Table 1.

[Example 10] In the production of the antifouling sheet, a tape-shaped polyethylene terephthalate substrate (manufactured by Toray Corporation, thickness 16μm) with smooth surfaces on both sides is used instead of the tape-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy-ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture protective film formation Composite sheet, evaluation of antifouling sheet, protective film formation film, and protective film formation composite sheet. The results are shown in Table 2.

[Example 11] In the production of the antifouling sheet, a tape-shaped polyethylene terephthalate substrate (made by Toray Corporation, thickness 12μm) with smooth surfaces on both sides is used instead of the tape-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy-ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture protective film formation Composite sheet, evaluation of antifouling sheet, protective film formation film, and protective film formation composite sheet. The results are shown in Table 2.

[Example 12] In the production of the antifouling sheet, a tape-shaped polyethylene terephthalate substrate (made by Toray Corporation, thickness 125μm) with smooth surfaces on both sides is used instead of the tape-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy-ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture protective film formation Composite sheet, evaluation of antifouling sheet, protective film formation film, and protective film formation composite sheet. The results are shown in Table 2.

[Example 13] In the production of the antifouling sheet, a strip-shaped polyethylene terephthalate substrate (manufactured by Toray Corporation, thickness 188μm) with smooth surfaces on both sides is used instead of the aforementioned strip-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy-ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture protective film formation Composite sheet, evaluation of antifouling sheet, protective film formation film, and protective film formation composite sheet. The results are shown in Table 2.

[Example 14] In the production of the antifouling sheet, a strip-shaped polyethylene terephthalate substrate (manufactured by Toyobo Co., Ltd., thickness 250μm) with smooth surfaces on both sides is used instead of the aforementioned tape-shaped polypropylene substrate (Mitsubishi Plastics Co., Ltd.) Manufacturing, thickness 80μm), one of the smooth surfaces was attached to the exposed surface of the non-energy ray-curable adhesive layer. Except for this point, the same method as in Example 1 was used to manufacture a protective film forming composite Sheets were evaluated for antifouling sheets, protective film formation films, and protective film formation composite sheets. The results are shown in Table 2.

[Comparative Example 1] [Manufacturing of protective film forming film] By the same method as in the case of Example 1, a strip-shaped laminated film formed by sequentially laminating these layers in the thickness direction of the first release film, the protective film forming film, and the second release film was produced.

[Evaluation of protective film formation film] [Evaluation of the visibility of laser printing of protective film formation film] The second release film is removed from the laminated film obtained above to obtain a laminate of the first release film and the protective film forming film. Then, using the same method as in the case of the composite sheet for forming a protective film with the first release film removed in the above-mentioned Example 1, the aforementioned laminate was attached to the inside of a semiconductor wafer with a diameter of 200 mm and a thickness of 350 μm. Whole face. Furthermore, the 1st peeling film was removed from the film for protective film formation. Then, a laminate of the protective film formation film and the semiconductor wafer is placed inside the laser printing device ("CSM3000" manufactured by EO Technics), and the protective film formation film attached to the semiconductor wafer is directly irradiated The laser light is used to perform laser printing on the surface (that is, the exposed surface) of the protective film forming film opposite to the semiconductor wafer side. At this time, the size of the printed characters is 0.3mm×0.2mm. In addition, the characters were directly visually observed, and the laser printing visibility of the protective film formation film was evaluated by the same method as in the case of Example 1. The results are shown in Table 2.

[Evaluation of antifouling property of protective film formation film] In the evaluation of the visibility of the laser printing of the protective film formation film described above, the exposed surface of the protective film formation film after laser printing was directly observed at the same time, and the protective film was evaluated by the same method as in the case of Example 1. The antifouling properties of the forming film. The results are shown in Table 2.

[Comparative Example 2] In the production of the antifouling sheet, a tape-shaped polypropylene substrate (manufactured by RIKEN TECHNOS, thickness 50μm) with an uneven surface on one side and a smooth surface on the other side is used instead of the tape-shaped polypropylene substrate (Mitsubishi Resin Made by the company, thickness 80μm), the uneven surface of the substrate is attached to the exposed surface of the non-energy-ray-curable adhesive layer, except for this point, the protective film is manufactured by the same method as in Example 1 The composite sheet for formation was evaluated for the antifouling sheet, the film for forming a protective film, and the composite sheet for forming the protective film. The results are shown in Table 2.

[Table 1] Example 1 2 3 4 5 6 7 8 9 Composition of composite sheet for forming protective film Film for forming protective film Hardening Thermosetting Thickness (μm) 15 Antifouling film Adhesive layer Hardening Non-energy ray hardening Energy ray hardening Non-energy ray hardening Thickness (μm) 10 On the forming surface of the substrate Concave and convex surface Smooth surface Concave and convex surface Smooth surface Substrate Main material PP PET PP PET Thickness (μm) 80 100 80 60 80 38 25 Maximum width (mm) 220 Relative to semiconductor wafer size ratio (%) 110 Evaluation results Clearness of antifouling sheet 420 430 450 440 155 210 40 450 450 15% elongation of anti-fouling sheet MD direction A A A A A A A A A TD direction A A A A A A A A A Tensile strength of anti-fouling sheet at 10% elongation (N/15mm) MD direction 13 13 13 170 18 5.9 13 64 40 TD direction 11 11 11 180 17 5.6 11 65 45 Visibility of laser printing of protective film formation film A A A A B A C A A Antifouling properties of the protective film formation film A A A A A A A A A Cutting suitability of composite sheet for forming protective film (number of sheets with burrs) A (0) A (0) A (0) A (0) A (0) B (2) A (0) A (0) A (0) Abrasion suppression of the blade of the cutter A A A A A A A A A

[Table 2] Example Comparative example 10 11 12 13 14 1 2 Composition of composite sheet for forming protective film Film for forming protective film Hardening Thermosetting Thickness (μm) 15 Antifouling film Adhesive layer Hardening Non-energy ray hardening - Non-energy ray hardening Thickness (μm) 10 - 10 On the forming surface of the substrate Smooth surface - Concave and convex surface Substrate Main material PET - PP Thickness (μm) 16 12 125 188 250 - 50 Maximum width (mm) 220 - 220 Relative to semiconductor wafer size ratio (%) 110 - 110 Evaluation results Clearness of antifouling sheet 460 460 440 440 430 - 210 15% elongation of anti-fouling sheet MD direction A A A A A - A TD direction A A A A A - A Tensile strength of anti-fouling sheet at 10% elongation (N/15mm) MD direction 26 twenty one 212 315 426 - 3.9 TD direction 27 twenty two 223 340 450 - 3.8 Visibility of laser printing of protective film formation film A A A A A A A Antifouling properties of the protective film formation film A A A A A B A Cutting suitability of composite sheet for forming protective film (number of sheets with burrs) A (0) A (0) A (0) A (0) A (0) - C (7) Abrasion suppression of the blade of the cutter A A B C D - A

It is obvious from the above results that in Examples 1 to 14, by using the antifouling sheet, when laser printing is performed on the protective film forming film, it is possible to prevent unexpected foreign matter from adhering to the protective film forming film. membrane. At this time, the strip-shaped composite sheet for forming a protective film can be installed inside the laminator without any problem. In addition, the aforementioned second laminate can be installed in the laser printing device without any problems.

Here, the antifouling performance of the protective film formation film during laser printing was evaluated, but the semiconductor wafer with the protective film formation composite sheet attached to the semiconductor wafer was subjected to operations other than laser printing (for example, transport, etc.) At the same time, the same thing is that the protective film forming film is also covered by the antifouling sheet. Therefore, it is obvious that in operations other than laser printing, the antifouling property of the protective film forming film is exhibited in the same manner as the above-mentioned laser printing.

Furthermore, in Examples 1 to 14, when the composite sheet for forming a protective film was stretched and attached to the semiconductor wafer, the antifouling sheet was not cut or wrinkled, and the protective film was formed The adhesiveness of the composite sheet is good. In addition, there is no burr on the cut surface of the protective film forming composite sheet, or the probability of burr generation is low, the generation of burrs is significantly suppressed, and the cutting suitability of the protective film forming composite sheet is good. In this way, since the composite sheet for forming a protective film in Examples 1 to 14 has good adhesion and cutting adaptability, it can be adjusted according to the size of the semiconductor wafer to be attached to the composite sheet for forming the protective film. The size of itself can be adjusted well by cutting, and it has characteristics suitable for the purpose of antifouling of the film for forming a protective film.

In Examples 1 to 14, the 15% extensibility of the test piece (anti-fouling sheet) was good in either the MD direction and the TD direction, and the test piece (anti-fouling sheet) did not break in the tensile test. And extend 15% or more in the tensile direction of the test piece (anti-fouling sheet).

In addition, in Examples 1 to 14, the tensile strength of the test piece (anti-fouling sheet) at 10% elongation in the MD direction is 5.9N/15mm or more (5.9N/15mm to 426N/15mm). The TD direction is 5.6N/15mm or more (5.6N/15mm to 450N/15mm), and the tensile strength is high in any direction. Among them, in Example 1 to Example 5 and Example 7, the aforementioned tensile strength is 13N/15mm or more in the MD direction (13N/15mm to 426N/15mm), and 11N/15mm or more in the TD direction (11N /15mm to 450N/15mm), the tensile strength is significantly high in either direction.

In this way, in Examples 1 to 14, the 15% elongation of the test piece (anti-fouling sheet) is good, and the tensile strength at 10% elongation of the test piece (anti-fouling sheet) is high. The characteristics of the composite sheet for forming a protective film are good.

In addition, in Examples 1 to 14, the antifouling sheet had a transparency of 40 or more (40 to 460). Among them, in Example 1 to Example 6, Example 8 to Example 14, the antifouling sheet has a high transparency of 155 or more (155 to 460). As a result, in these examples, the protective film forming composite sheet The film for forming a protective film is excellent in laser printing visibility. The composite sheet for forming a protective film of Example 7 can be sufficiently used for applications where laser printing is not performed on the film for forming a protective film or the protective film.

On the other hand, in Examples 1 to 13, the tensile strength of the test piece (anti-fouling sheet) at 10% elongation in the MD direction is 315N/15mm or less (5.9N/15mm to 315N/15mm), In the TD direction, it is 340N/15mm or less (5.6N/15mm to 340N/15mm). In Example 1 to Example 13, the tensile strength in either the MD direction and the TD direction is within a specific range, so that when the protective film forming composite sheet is cut, the cutting is used The abrasion of the blade of the cutter is suppressed, and the abrasion suppression is good. In particular, in Examples 1 to 11, the tensile strength of the test piece (anti-fouling sheet) at 10% elongation in the MD direction is 170N/15mm or less (5.9N/15mm to 170N/15mm), The TD direction is 180N/15mm or less (5.6N/15mm to 180N/15mm), and the tensile strength in either direction of the MD direction and the TD direction is further within a specific range, thereby forming a composite sheet for protective film At the time of cutting, the abrasion of the blade of the cutter used in the cutting is significantly suppressed, and the abrasion suppression is particularly excellent. In this way, the composite sheets for forming a protective film of Examples 1 to 13 have more excellent characteristics.

In contrast, in Example 14, the tensile strength of the test piece (anti-fouling sheet) at 10% elongation was greater in either the MD direction and the TD direction than in the other examples. Therefore, in Example 14, when the composite sheet for forming a protective film was cut, the blade of the cutter used for the cut was significantly worn. However, the cutting itself of the composite sheet for forming a protective film at this time can be performed without any problem, and the composite sheet for forming a protective film can be continuously cut by replacing the blade of the cutter.

On the other hand, in Comparative Example 1, the antifouling sheet was not used. Therefore, when laser printing was performed on the protective film forming film, it was not possible to prevent unexpected foreign matter from adhering to the protective film forming film. In this way, when the anti-fouling sheet is not used, when performing operations other than laser printing (for example, transport, etc.) on the semiconductor wafer with the protective film forming film, the same thing is that the protective film forming film is not covered by the anti-fouling The film is covered and exposed. Therefore, it is obvious that in operations other than laser printing, the antifouling property of the protective film forming film is not exerted in the same manner as the above-mentioned laser printing.

In Comparative Example 2, by using the antifouling sheet, when laser printing is performed on the protective film forming film, it is possible to prevent unintended foreign matter from adhering to the protective film forming film. However, in the cut surface of the composite sheet for forming a protective film, the generation rate of burrs is high, the generation of burrs is not significantly suppressed, and the cutting suitability of the composite sheet for forming a protective film is poor. In this way, the composite sheet for forming a protective film of Comparative Example 2 was poor in cutting suitability, and therefore, it was not possible to adjust itself well by cutting according to the size of the semiconductor wafer to be attached to the composite sheet for forming a protective film. The size does not have the characteristics suitable for the antifouling purpose of the protective film forming film.

In Comparative Example 2, the tensile strength of the test piece (anti-fouling sheet) at 10% elongation is 3.9N/15mm in the MD direction and 3.8N/15mm in the TD direction, and the tensile strength is low in either direction . In this way, in Comparative Example 2, the tensile strength at 10% elongation of the test piece (anti-fouling sheet) was low, and it is estimated that the cutting suitability of the composite sheet for forming a protective film as described above was poor. [Industry Availability]

The present invention can be used to manufacture semiconductor devices.

7: Pull-off mechanism 8: Adhesive sheet 9: Semiconductor wafer 9a: Circuit formation surface of semiconductor wafer 9b: Inner surface of semiconductor wafer (attachment surface with protective film forming composite sheet) 9': Semiconductor wafer 9a ': the circuit formation surface of the semiconductor wafer 9b': the inner surface of the semiconductor wafer 10, 20: the antifouling sheet 10a, 20a: the first side of the antifouling sheet 10b: the second side of the antifouling sheet 11: the base material 11a: the base The first surface of the material 11b: the second surface of the substrate 12: the adhesive layer 12a: the first surface of the adhesive layer 13: the protective film formation film 13a: the first surface of the protective film formation film 13b: the protective film formation The second side of the film 13': the protective film 13a': the first side of the protective film 13b': the second side of the protective film 15: the release film 23: the protective film forming film (protective film) 23a: the protective film forming The first surface 23b of the film (protective film): the second surface of the film (protective film) for forming a protective film 91, 92: the semiconductor wafer with a protective film 101, 101', 102, 103, 111, 1111: the composite sheet for forming a protective film 101a, 102a , 103a: The attaching surface to the semiconductor wafer in the protective film forming composite sheet 130', 230: The cut protective film 130a', 230a: The first surface of the cut protective film 130b', 230b: After cutting The second side of the protective film 810: Laminated sheet 901, 904 including anti-fouling sheet and adhesive sheet: 1st laminated body 901', 902', 904': 2nd laminated body 902, 905: Laser-printed second laminated body 903, 906 : Semiconductor chip group with protective film L: Laser light W ₉ : Width of semiconductor wafer W ₁₀₁ , W ₁₀₂ , W ₁₀₃ , W ₁₁₁ : Width of composite sheet for protective film formation W ₁₀₁ ', W ₁₀₃ ': After cutting The width of the composite sheet for forming a protective film

Fig. 1 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention. [FIG. 2] A plan view schematically showing an example of a composite sheet for forming a protective film whose planar shape is a rectangular shape or a belt shape. Fig. 3 is a plan view schematically showing an example of a composite sheet for forming a protective film whose planar shape is another shape. Fig. 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to an embodiment of the present invention. [FIG. 5A] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 5B] A cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 5C] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 5D] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 6A] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 6B] A cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 6C] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 7A] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 7B] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 7C] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 8A] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 8B] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention. [FIG. 8C] is a cross-sectional view for schematically explaining an example of a method of manufacturing a semiconductor wafer with a protective film according to an embodiment of the present invention.

10: Anti-fouling sheet

10a: The first side of the anti-fouling sheet

11: Substrate

11a: The first side of the substrate

11b: The second side of the substrate

12: Adhesive layer

12a: The first side of the adhesive layer

13: Film for forming protective film

13a: The first side of the protective film formation film

15: Peel off the film

101: Composite sheet for protective film formation

101a: The attaching surface to the semiconductor wafer in the composite sheet for forming a protective film

W ₁₀₁ : Width of the composite sheet for forming a protective film

Claims (5)

A composite sheet for forming a protective film, which is used for attaching to the inner surface of a semiconductor wafer to form a protective film on the aforementioned inner surface; The aforementioned composite sheet for forming a protective film includes an antifouling sheet and a film for forming a protective film formed on one side of the aforementioned antifouling sheet; The aforementioned protective film forming film can form the aforementioned protective film; The maximum width of the composite sheet for forming a protective film in a direction parallel to the attaching surface of the semiconductor wafer in the composite sheet for forming a protective film is 155mm to 194mm, 205mm to 250mm, 305mm to 350mm , Or 455mm to 500mm; A test piece of the aforementioned antifouling sheet with a width of 15mm was produced, and the following tensile test was carried out, that is, under the temperature condition of 18°C to 28°C, the initial chuck spacing was set to 100mm, and the aforementioned test piece was relative to When the surface of the test piece is stretched in a parallel direction at a speed of 200 mm/min, the test piece can be elongated by 15% or more, and the tensile strength of the test piece when it is extended by 10% is 4.0 N/15mm or more. The composite sheet for forming a protective film according to claim 1, wherein the antifouling sheet is used to prevent unexpected foreign matter from adhering to the inner surface of the semiconductor wafer when the composite sheet for forming the protective film is used The aforementioned protective film formation film. The composite sheet for forming a protective film according to claim 1 or 2, wherein the antifouling sheet has a transparency of 100 or more. A method for manufacturing a semiconductor chip with a protective film, which is to manufacture a semiconductor chip with a protective film formed by a semiconductor chip and a protective film provided on the inner surface of the aforementioned semiconductor chip; The aforementioned protective film is formed of the protective film formation film in the composite sheet for protective film formation as described in any one of claims 1 to 3; When the protective film formation film is curable, the cured product of the protective film formation film is a protective film, and when the protective film formation film is non-curable, it is attached to the divided semiconductor wafer The aforementioned protective film forming film behind the inner surface of the previous semiconductor wafer is a protective film; The aforementioned manufacturing method of a semiconductor chip with a protective film has the following steps: The first attaching step is to stretch the composite sheet for forming a protective film in a direction parallel to the attaching surface of the semiconductor wafer in the composite sheet for forming a protective film, while stretching the protective film The protective film forming film in the forming composite sheet is attached to the entire inner surface of the semiconductor wafer that is smaller in size than the protective film forming film, and the protective film is formed on the inner surface of the semiconductor wafer. Use the first layered body of the composite sheet; The first cutting step is to cut the composite sheet for forming the protective film in the first laminate along the outer periphery of the semiconductor wafer, thereby preparing the semiconductor wafer with the cut The second laminate of the composite sheet for forming a protective film; The operation step is to operate the aforementioned second layered body; The second attaching step is to attach the adhesive sheet to the surface of the antifouling sheet in the second laminate after the operation on the side opposite to the side of the protective film forming film or the protective film after the operation. ； The dividing step is after the second attaching step, dividing the semiconductor wafer to produce a semiconductor wafer; The second cutting step is to cut the protective film forming film or protective film after the second attaching step; and In the picking step, the semiconductor wafer provided with the cut protective film forming film or the protective film is separated from the laminated sheet containing the antifouling sheet and the adhesive sheet to be picked up; In the first attaching step, the maximum width of the composite sheet for forming a protective film in a direction parallel to the attaching surface of the semiconductor wafer in the composite sheet for forming a protective film is made, The maximum width of the semiconductor wafer in the direction parallel to the attachment surface of the protective film forming composite sheet in the semiconductor wafer is 101.1% to 129.3%; When the film for forming a protective film is curable, a curing step is further provided. After the above-mentioned operation step, the film for forming a protective film is cured to form a protective film. The method for manufacturing a semiconductor wafer with a protective film described in claim 4, wherein the above-mentioned operation step is a printing step of printing by irradiating the film for forming a protective film in the second layered body with laser light.

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